EP0790076B1 - Catalysts containing metallocenes with arylsubstituted indenyl derivatives as ligands, process and intermediates for the preparation of these metallocenes and their use - Google Patents

Abstract

Catalysts consisting of a metallocene of formula (I) and a cocatalyst are claimed, M<1> = a Group IVb, Vb or VIb metal; R<1>, R<2> = H, 1-10C alkyl or alkoxy, 6-10C aryl or aryloxy, 2-10C alkenyl, 7-40C aralkyl or alkaryl, 8-40C aralkenyl, OH or halogen; R<3> = H, halogen, optionally halogenated 1-10C alkyl, 6-10C aryl, N(R<16>)2, SR<16>, OSi(R<16>)3, Si(R<16>)3 or P(R<16>)2 (with R<16> = halogen, 1-10C alkyl or 6-10C aryl); R<4>-R<12> = as for R<3>, or adjacent groups may form part of one or more aromatic or aliphatic rings, or the groups R<5> and R<8> or R<12> may form such rings with the attached atoms; R<13> = -X-, -X-X-, -Y-Y-, -O-X-O- -Y-, -O-X-, -Y-X-, -Y-Y-Y-, =BR<14>, =AlR<14>, -O-, -S-, =SO, =SO2, =NR<14>, =CO, =PR<14> or =P(O)R<14>; X = -M<2>R<14>R<15>-; Y = -CR<14>R<15>; R<14>, R<15> = H, halogen, 1-10C alkyl, fluoroalkyl or alkoxy, 6-10C aryl, fluoroaryl or aryloxy, 2-10C alkenyl, 7-40C aralkyl or alkaryl, or 8-40C aralkenyl, or R<14> + R<15> + the attached atoms may form ring(s); M<2> = silicon, germanium or tin. Also claimed are: (i) polyolefins obtained by (co)polymerisation of olefins of formula Ra-CH=CH-Rb (with Ra, Rb = H or 1-14C hydrocarbyl, or Ra + Rb may form part of one or more rings) at -60 to 200 degrees C and 0.5-100 bar in solution, suspension or gas phase, in presence of these catalysts; (ii) a process for the production of metallocenes (I); and (iii) intermediate indanones, indenes and bridged ligand systems formed in this process.

Description

The present invention relates to new aryl-substituted metallocenes Indenyl derivatives as ligands, which are very advantageous as catalyst components in the Production of polyolefins with high isotacticity, narrow molecular weight distribution and very high molecular weight can be used.

High molecular weight polyolefins are particularly important for production of foils, plates or large hollow bodies or molded parts, such as pipes.

The production of polyolefins with soluble metallocene compounds is known from the literature in combination with aluminoxanes or other cocatalysts convert the neutral metallocene into a cation due to its Lewis acidity and can stabilize, known.

Soluble metallocene compounds based on bis (cyclopentadienyl) zirconium dialkyl or dihalide in combination with oligomeric aluminoxanes can ethylene with Polymerize good and propylene with moderate activity. Polyethylene is obtained with narrow molecular weight distribution and medium molecular weight. The manufactured in this way Polypropylene is atactic and has a very low molecular weight.

Isotactic polypropylene can be produced with the aid of ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride together with an aluminoxane in a suspension polymerization (cf. EP-A-185 918). The polymer has a tight Molar mass distribution. A particular disadvantage of this method is that with technical relevant polymerization temperatures only polymers with very low molecular weight can be produced.

A special pre-activation method of the metallocene with a Aluminoxan proposed, which leads to a considerable increase in the activity of the Catalyst system and to a significant improvement in the grain morphology of the Polymer leads (see. DE 37 26 067). The preactivation increases the molecular weight not essential.

Furthermore, catalysts based on ethylene bisindenyl hafnium dichloride and ethylene bis (4,5,6,7-tetrahydro-1-indenyl) hafnium dichloride and methylaluminoxane are known, with which higher molecular weight polypropylenes can be produced by suspension polymerization (cf. J. Am. Chem. Soc. (1987) 109 , 6544). Under technically relevant polymerization conditions, however, the commorphology of the polymers produced in this way is unsatisfactory and the activity of the catalyst systems used is comparatively low. Coupled with the high catalyst costs, low-cost polymerization is therefore not possible with these systems.

A significant increase in the molar mass could be achieved by using metallocenes in which the aromatic π ligands fixed by a bridge are in the 2-position (see DE 40 35 886) or in the 2- and 4-position (see DE 41 28 238) bear substituents.

A further increase in the molecular weight was achieved by using aromatic π ligands with substituents in the 2-, 4- and 6-position (see DE 41 39 596) and aromatic π ligands of the 4,5-benzoindenyl type (see DE 41 39 595).

The latter metallocenes with the substituents mentioned are in this In terms of a polymerization temperature of 70 ° C already very powerful. Nevertheless, the molar masses that can be achieved are at the technically optimal polymerization temperature of 70 ° C for many technical applications such as Production of polymers for tubes and large hollow bodies as well as special fibers still too low. Also those disclosed in EP 0 485 823 A1 Metallocenes do not yet provide polymers that have a large molecular weight range have high melting points. Under the constraint of large-scale, cost-effective production must be possible high reaction temperatures are polymerized because at higher polymerization temperatures the resulting heat of reaction is dissipated with less cooling medium can be. Therefore, the cooling water circuit can be dimensioned significantly smaller become.

A common disadvantage of soluble (homogeneous) metallocene / methylaluminoxane catalyst systems in processes in which the polymer formed is a solid is the formation of thick deposits on the reactor walls and stirrers. This Coatings arise from agglomeration of the polymer particles when the metallocene, or aluminoxane, or both are present dissolved in the suspension medium. Such Deposits in the reactor systems must be removed regularly, as these are quick achieve considerable strengths, have high strength and heat exchange to prevent coolant.

It is therefore advantageous to use metallocenes in a supported form. An efficient one and simple process for the support of metallocenes, which is universal in all Polymerization process can be used has been proposed (see EP-A-578 838).

Another disadvantage in the case of stereospecific polymerization of prochiral monomers, e.g. of propylene, with metallocene catalysts is the relatively low isotaxy, which affects low melting points in the case of isotactic polypropylene. In particular metallocenes with substituents in the 2- and 4-position and especially rac-dimethylsilylbis (2-methyl-4-isopropyl-indenyl) zirconium dichloride in combination with In the case of propylene, methylaluminoxane provide a polymer with high isotacticity and therefore high melting point (cf. EP-A-530 647). Nevertheless, the achievable Melting points at technically relevant polymerization temperatures (e.g. 70 ° C) for some technical applications too low.

However, there are also technical applications where low melting points are desired.

The task was to find a process and / or a catalyst system that Polymers with very high molecular weight and in the case of isospecific polymerization prochiral monomeric polymers with high isotaxy produced in high yield. By Carrying could cause the disadvantages known from the prior art The formation of deposits and a high proportion of fine grains can be avoided. By using Hydrogen as a molecular weight regulator should then cover the entire technical area interesting molar masses can be covered with just one metallocene.

It has now been found that metallocenes with special indenyl derivatives as Ugands suitable catalysts (catalyst components) in the production of polyolefins with high molecular weight, especially when using prochiral monomers of areotactic polyolefins with very high molecular weight and very high isotaxy.

By reacting these soluble metallocenes with a supported organoaluminum Catalyst component creates a catalyst system that is used for activation no additional cocatalyst required and the formation of reactor coatings completely avoided.

worin

M¹ ein Metall der Gruppe IVb, Vb oder VIb des Periodensystems ist,

R¹ und R² gleich oder verschieden sind und ein Wasserstoffatom, eine C₁-C₁₀-Alkyl-, eine C₁-C₁₀-Alkoxy-, eine C₆-C₁₀-Aryl-, eine C₆-C₁₀-Aryloxy-, eine C₂-C₁₀-Alkenyl-, eine C₇-C₄₀-Arylalkyl-, eine C₇-C₄₀-Alkylaryl-, eine C₈-C₄₀-Arylalkenyl-, eine OH-Gruppe oder ein Halogenatom bedeuten,

die Reste R³ gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom, eine C₁-C₁₀-Alkylgruppe, die halogeniert sein kann, eine C₆-C₁₀-Arylgruppe, einen NR¹⁶ ₂-, -SR¹⁶-, -OSiR¹⁶ ₃-, -SiR¹⁶ ₃- oder -PR¹⁶ ₂-Rest bedeuten, worin R¹⁶ ein Halogenatom, eine C₁-C₁₀-Alkylgruppe oder eine C₆-C₁₀-Arylgruppe ist,

R⁴ bis R¹² gleich oder verschieden sind und die für R³ genannten Bedeutungen besitzen, oder benachbarte Reste R⁴ bis R¹² mit den sie verbindenden Atomen einen oder mehrere aromatische oder aliphatische Ringe bilden, oder die Reste R⁵ und R⁸ oder R¹² mit den sie verbindenden Atomen einen aromatischen oder aliphatischen Ring bilden,

R¹³

=BR¹⁴, =AIR¹⁴, -Ge-, -O-, -S-, =SO, =SO₂, =NR¹⁴, =CO, =PR¹⁴ oder =P(O)R¹⁴ ist,

wobei R¹⁴ und R¹⁵ gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom, eine C₁-C₁₀-Alkyl-, eine C₁-C₁₀-Fluoralkyl-, eine C₁-C₁₀-Alkoxy-, eine C₆-C₁₀-Aryl-, eine C₆-C₁₀-Fluoraryl-, eine C₆-C₁₀-Aryloxy-, eine C₂-C₁₀-Alkenyl-, eine C₇-C₄₀-Arylalkyl-, eine C₇-C₄₀-Alkylaryl-, eine C₈-C₄₀-Arylalkenylgruppe bedeuten, oder

R¹⁴ und R¹⁵ jeweils mit den sie verbindenden Atomen einen oder mehrere Ringe bilden und

M² Silizium, Germanium oder Zinn ist.

The present invention therefore relates to compounds of the formula I:

wherein

M ^{1 is} a metal from group IVb, Vb or VIb of the periodic table,

R ¹ and R ^{2 are} identical or different and are a hydrogen atom, a C ₁ -C ₁₀ alkyl, a C ₁ -C ₁₀ alkoxy, a C ₆ -C ₁₀ aryl, a C ₆ -C ₁₀ - Aryloxy, a C ₂ -C ₁₀ alkenyl, a C ₇ -C ₄₀ arylalkyl, a C ₇ -C ₄₀ alkylaryl, a C ₈ -C ₄₀ arylalkenyl, an OH group or a halogen atom mean,

the radicals R ^{3 are} identical or different and are a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group which may be halogenated, a C ₆ -C ₁₀ aryl group, an NR ¹⁶ ₂ -, -SR ¹⁶ -, - OSiR ¹⁶ ₃ -, -SiR ¹⁶ ₃ - or -PR ¹⁶ ₂ radical, in which R ^{16 is} a halogen atom, a C ₁ -C ₁₀ alkyl group or a C ₆ -C ₁₀ aryl group,

R ⁴ to R ^{12 are the} same or different and have the meanings given for R ³ , or neighboring radicals R ⁴ to R ^{12 form} one or more aromatic or aliphatic rings with the atoms connecting them, or the radicals R ⁵ and R ⁸ or R ¹² form an aromatic or aliphatic ring with the atoms connecting them,

R ¹³

= BR ¹⁴ , = AIR ¹⁴ , -Ge-, -O-, -S-, = SO, = SO ₂ , = NR ¹⁴ , = CO, = PR ¹⁴ or = P (O) R ¹⁴ ,

wherein R ¹⁴ and R ^{15 are the} same or different and are a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl, a C ₁ -C ₁₀ fluoroalkyl, a C ₁ -C ₁₀ alkoxy, a C ₆ -C ₁₀ aryl, a C ₆ -C ₁₀ fluoroaryl, a C ₆ -C ₁₀ aryloxy, a C ₂ -C ₁₀ alkenyl, a C ₇ -C ₄₀ arylalkyl, a C ₇ -C ₄₀ alkylaryl, a C ₈ -C ₄₀ arylalkenyl group, or

R ¹⁴ and R ¹⁵ each form one or more rings with the atoms connecting them and

M ^{2 is} silicon, germanium or tin.

The present invention also relates to a process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula R ^a -CH = CH-R ^b , in which R ^a and R ^{b are} identical or different and a hydrogen atom or a hydrocarbon radical with 1 to 14 C. -Atoms mean, or R ^a and R ^b can form one or more rings with the atoms connecting them, at a temperature of -60 to 200 ° C, at a pressure of 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst which is formed from a metallocene as transition metal compound and a cocatalyst, characterized in that the metallocene is a compound of the formula I.

worin M¹ ein Metall der Gruppe IVb, Vb oder Vlb des Periodensystems, beispielsweise Titan, Zirkonium, Hafnium, Vanadium, Niob, Tantal, Chrom, Molybdän oder Wolfram, vorzugsweise Zirkonium, Hafnium und Titan ist. The compounds according to the invention are metallocenes of the formula I.

wherein M ^{1 is} a metal from group IVb, Vb or Vlb of the periodic table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium and titanium.

R ¹ and R ² are the same or different and represent a hydrogen atom, a C ₁ -C ₁₀ , preferably C ₁ -C ₃ alkyl group, a C ₁ -C ₁₀ , preferably C ₁ -C ₃ alkoxy group, a C. ₆ -C ₁₀ -, preferably C ₆ -C ₈ aryl group, a C ₆ -C ₁₀ -, preferably C ₆ -C ₈ aryloxy group, a C ₂ -C ₁₀ -, preferably C ₂ -C ₄ alkenyl group, a C ₇ -C ₄₀ -, preferably C ₇ -C ₁₀ arylalkyl group, a C ₇ -C ₄₀ -, preferably C ₇ -C ₁₂ alkylaryl group, a C ₈ -C ₄₀ -, preferably C ₈ -C ₁₂ arylalkenyl group, or a halogen atom, preferably chlorine.

The radicals R ³ to R ¹² are the same or different and represent a hydrogen atom, a halogen atom, preferably fluorine, chlorine or bromine, a C ₁ -C ₁₀ -, preferably C ₁ -C ₄ -alkyl group, which can be halogenated, a C. ₆ -C ₁₀ -, preferably C ₆ -C ₈ aryl group, a - NR ¹⁶ ₂ -, -SR ¹⁶ -, -OSiR ¹⁶ ₃ -, -SiR ¹⁶ ₃ - or -PR ¹⁶ ₂ radical, where R ^{16 is} a Halogen atom, preferably chlorine, or a C ₁ -C ₁₀ , preferably C ₁ -C ₄ alkyl group or a C ₆ -C ₁₀ , preferably C ₆ -C ₈ aryl group.

R¹³ ist

=BR¹⁴, =AIR¹⁴, -Ge-, -O-, -S-, =SO, =SO₂, =NR¹⁴, =CO, =PR¹⁴ oder =P(O)R¹⁴, vorzugsweise

=BR¹⁴, =AIR¹⁴, -Ge-, -O-, -S-, =SO, =SO₂, =NR¹⁴, =CO, =PR¹⁴, oder =P(O)R¹⁴, wobei R¹⁴ und R¹⁵ gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom, eine C₁-C₁₀-, vorzugsweise C₁-C₄-Alkylgruppe insbesondere Methylgruppe, eine C₁-C₁₀-Fluoralkyl-, vorzugsweise CF₃-Gruppe, eine C₆-C₁₀-, vorzugsweise C₆-C₈-Aryl-, eine C₆- C₁₀-Fluoraryl-, vorzugsweise Pentafluorphenylgruppe, eine C₁-C₁₀-, vorzugsweise C₁-C₄-Alkoxygruppe, insbesondere Methoxygruppe, eine C₂-C₁₀-, vorzugsweise C₂-C₄-Alkenylgruppe, eine C₇-C₄₀-, vorzugsweise C₇-C₁₀-Arylalkylgruppe, eine C₈-C₄₀-, vorzugsweise C₈-C₁₂-Arylalkenylgruppe, eine C₇-C₄₀-, vorzugsweise C₇-C₁₂-Alkylarylgruppe bedeuten oder R¹⁴ und R¹⁵ jeweils mit den sie verbindenden Atomen einen Ring bilden.

M² ist Silizium, Germanium oder Zinn, vorzugsweise Silizium oder Germanium.

Für Verbindungen der Formel I gilt bevorzugt, daß

M¹ Zirkonium oder Hafnium ist,

R¹ und R² gleich sind und eine C₁-C₃-Alkylgruppe oder ein Halogenatom bedeuten, die Reste R³ gleich sind und eine C₁-C₄-Alkylgruppe bedeuten,

R⁴ bis R¹² gleich oder verschieden sind und Wasserstoff oder eine C₁-C₄-Alkylgruppe bedeuten,

R¹³ für

steht, wobei M² Silizium oder Germanium ist und R¹⁴ und R¹⁵ gleich oder verschieden sind und für eine C₁-C₄- Alkylgruppe oder eine C₆-C₁₀-Arylgruppe stehen.

The adjacent radicals R ⁴ to R ¹² can form an aromatic, preferably 6-membered aromatic or aliphatic, preferably 4-8-membered aliphatic ring with the atoms connecting them.

R ¹³ is

= BR ¹⁴ , = AIR ¹⁴ , -Ge-, -O-, -S-, = SO, = SO ₂ , = NR ¹⁴ , = CO, = PR ¹⁴ or = P (O) R ¹⁴ , preferably

= BR ¹⁴ , = AIR ¹⁴ , -Ge-, -O-, -S-, = SO, = SO ₂ , = NR ¹⁴ , = CO, = PR ¹⁴ , or = P (O) R ¹⁴ , where R ¹⁴ and R ^{15 are} identical or different and are a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ , preferably C ₁ -C ₄ alkyl group, in particular methyl group, a C ₁ -C ₁₀ fluoroalkyl, preferably CF ₃ group C ₆ -C ₁₀ -, preferably C ₆ -C ₈ -aryl, a C ₆ - C ₁₀ -Fluoraryl-, preferably pentafluorophenyl group, a C ₁ -C ₁₀ -, preferably C ₁ -C ₄ alkoxy, in particular methoxy, a C ₂ -C ₁₀ , preferably C ₂ -C ₄ alkenyl group, a C ₇ -C ₄₀ , preferably C ₇ -C ₁₀ arylalkyl group, a C ₈ -C ₄₀ , preferably C ₈ -C ₁₂ arylalkenyl group mean a C ₇ -C ₄₀ , preferably C ₇ -C ₁₂ alkylaryl group or R ¹⁴ and R ¹⁵ each form a ring with the atoms connecting them.

M ² is silicon, germanium or tin, preferably silicon or germanium.

For compounds of formula I it is preferred that

M ^{1 is} zirconium or hafnium,

R ¹ and R ^{2 are} identical and denote a C ₁ -C ₃ alkyl group or a halogen atom, the radicals R ^{3 are} identical and denote a C ₁ -C ₄ alkyl group,

R ⁴ to R ^{12 are} identical or different and denote hydrogen or a C ₁ -C ₄ alkyl group,

R ¹³ for

stands, wherein M ^{2 is} silicon or germanium and R ¹⁴ and R ^{15 are} identical or different and stand for a C ₁ -C ₄ alkyl group or a C ₆ -C ₁₀ aryl group.

Also preferred are compounds of the formula I in which the radicals R ⁴ and R ^{7 are} hydrogen and R ⁵ , R ⁶ and R ⁸ to R ^{12 are} a C ₁ -C ₄ alkyl group or hydrogen.

steht, wobei M² Silizium bedeutet, und R¹⁴ und R¹⁵ gleich oder verschieden sind und für eine C₁-C₄-Alkylgruppe oder eine C₆-C₁₀-Arylgruppe stehen.Particularly preferred are compounds of the formula I in which M ^{1 is} zirconium, R ¹ and R ^{2 are the} same and are chlorine, the radicals R ^{3 are the} same and represent a C ₁ -C ₄ alkyl group, R ⁴ and R ^{7 are} hydrogen R ⁵ , R ⁶ and R ⁸ to R ^{12 are} identical or different and are a C ₁ -C ₄ alkyl group or hydrogen and R ^{13 is}

stands, where M ^{2 is} silicon, and R ¹⁴ and R ^{15 are} identical or different and represent a C ₁ -C ₄ alkyl group or a C ₆ -C ₁₀ aryl group.

X = nukleophile Abgangsgruppe, beispielsweise Halogen oder Tosyl.

The metallocenes I are prepared by processes known from the literature and are reproduced in the reaction scheme below

X = nucleophilic leaving group, for example halogen or tosyl.

The 2-phenyl-benzyl halide derivatives of the formula A are commercially available or can be produced by methods known from the literature.

The conversion to the compounds of formula B takes place by reaction with substituted ones Malonic esters under basic conditions, such as in ethanolic solutions of sodium ethanolate.

The compounds of formula B are mixed with alkali hydroxides such as potassium hydroxide or Saponified sodium hydroxide and by treating the resulting dicarboxylic acids with Heat decarboxylated to the compounds of formula C.

The ring closure to the corresponding phenyl-1-indanones of the formula D is carried out by reaction with chlorinating agents such as SOCl ₂ to give the corresponding acid chlorides and subsequent cyclization with a Friedel-Crafts catalyst in an inert solvent such as AICl ₃ or polyphosphoric acid in methylene chloride or CS ₂ .

The conversion to the 7-phenyl-indene derivatives of the formula E takes place by reduction with a hydride transferring reagent, such as sodium borohydride or Lithium aluminum hydride or hydrogen and a corresponding catalyst in an inert solvent such as diethyl ether or tetrahydrofuran the corresponding alcohols and dehydration of the alcohols under acidic Conditions such as p-toluenesulfonic acid or an aqueous mineral acid or by reaction with dehydrating substances such as magnesium sulfate, anhydrous copper sulfate or molecular sieves.

The preparation of the ligand systems of formula G and the implementation of the bridged chiral metallocenes of the formula H and the isolation of the desired Racemic form is known in principle. For this, the phenolene derivative of Formula E with a strong base such as butyllithium or potassium hydride in deprotonated with an inert solvent and with a reagent of formula F. implemented the ligand system of formula G. This is then done with two Equivalents of a strong base such as butyllithium or potassium hydride in deprotonated with an inert solvent and with the corresponding metal tetra-olefin polymerization. The chiral metallocenes are preferably used as a racemate. However, the pure enantiomer in the (+) or (-) form can also be used. An optically active polymer can be produced with the pure enantiomers. Detached However, the meso form of the metallocenes should be used, since the polymerization-active Center (the metal atom) in these compounds because of mirror symmetry is no longer chiral on the central metal atom and is therefore not a highly isotactic polymer can generate. If the meso form is not separated, isotactic forms arise Polymers also atactic polymer. For certain applications, for example soft moldings, this can be quite desirable.

According to the invention, an aluminoxane of the formula IIa for the linear type and / or of the formula IIb for the cyclic type is preferably used as cocatalyst,

If the R ¹⁷ radicals are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, with hydrogen or isobutyl preferably containing 0.01-40% (number of the R ¹⁷ radicals).

The aluminoxane can be prepared in various ways by known methods. One of the methods is, for example, that an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as toluene). To produce an aluminoxane with different radicals R ¹⁷ , for example, two different aluminum trialkyls are reacted with water in accordance with the desired composition.

The exact structure of the aluminoxanes IIa and IIb is not known.

Regardless of the type of manufacture, all aluminoxane solutions are changing Content of unreacted aluminum starting compound, which in free form or is present as an adduct, together.

It is possible to include the metallocene in the polymerization reaction before use preactivate an aluminoxane of the formula IIa and / or IIb. This will make the Polymerization activity increased significantly and the grain morphology improved. The The transition metal compound is preactivated in solution. Prefers the metallocene is in a solution of the aluminoxane in an inert Dissolved hydrocarbon. An aliphatic hydrocarbon is suitable as the inert hydrocarbon or aromatic hydrocarbon. Toluene is preferably used.

The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total amount of solution. The metallocene can be used in the same concentration, but preferably it is used in an amount of 10 ^-4 - 1 mol per mol of aluminoxane. The preactivation is 5 minutes to 60 hours, preferably 5 to 60 minutes. One works at a temperature of -78 to 100 ° C, preferably 0 to 70 ° C.

A prepolymerization can be carried out using the metallocene. For prepolymerization preference is given to (or one of the) olefin (s) used in the polymerization used.

The metallocene can also be applied to a support. Suitable carrier materials are, for example, silica gels, aluminum oxides, solid aluminoxane or others inorganic carrier materials such as magnesium chloride. On A suitable carrier material is also a polyolefin powder in finely divided form.

Preferably the cocatalyst, i.e. the organoaluminum compound a carrier such as silica gels, aluminum oxides, solid aluminoxane, others inorganic carrier materials or a polyolefin powder in finely divided form applied and then implemented with the metallocene.

Oxides that are flame-pyrolytic can be used as inorganic carriers generated by burning element halides in a detonating gas flame were, or as silica gels in certain grain size distributions and grain shapes are producible.

The supported cocatalyst can be prepared, for example, as in EP-A-578 838 described in the following manner in a stainless steel reactor explosion-proof version with a pumping system of pressure level 60 bar, with inert gas supply, temperature control through jacket cooling and second cooling circuit via a heat exchanger on the pump system. The pump system sucks the reactor contents via a connection in the reactor bottom with a pump and presses it into a mixer and through a riser pipe via a heat exchanger the reactor back. The mixer is designed so that there is a constricted in the inlet Pipe cross-section is located where there is an increased flow velocity, and in whose turbulence zone has a thin feed line axially and counter to the direction of flow is guided, through which - clocked - a defined amount of water each 40 bar argon can be fed. The reaction is controlled via a Sampler on the pump circuit.

In principle, however, other reactors are also suitable.

In the above-described reactor with 16 dm ³ volume, 5 dm ³ decane are placed under inert conditions. 0.5 dm ³ (= 5.2 mol) trimethyl aluminum are added at 25 ° C. Then 250 g of silica gel SD 3216-30 (Grace AG), which had previously been dried in an argon fluid bed at 120 ° C., are metered into the reactor through a solids funnel and homogeneously distributed using the stirrer and the pumping system. A total of 76.5 g of water is added to the reactor in portions of 0.1 cm ³ for 3.25 h every 15 s. The pressure, resulting from the argon and the evolved gases, is kept constant at 10 bar by a pressure control valve. After all the water has been introduced, the pumping system is switched off and stirring is continued at 25 ° C. for 5 hours.

The supported cocatalyst produced in this way is used as a 10% suspension in n-decane. The aluminum content is 1.06 mmol Al per cm ³ suspension. The isolated solid contains 31% by weight of aluminum, the suspension medium contains 0.1% by weight of aluminum.

Further possibilities for the production of a supported cocatalyst are in EP-A-578 838.

Thereafter, the metallocene according to the invention on the supported cocatalyst applied by stirring the dissolved metallocene with the supported cocatalyst becomes. The solvent is removed and replaced by a hydrocarbon in which both the cocatalyst and the metallocene are insoluble.

The reaction to the supported catalyst system takes place at a temperature of -20 ° to + 120 ° C, preferably 0-100 ° C, particularly preferably at 15 ° to 40 ° C. The Metallocene is reacted with the supported cocatalyst in such a way that the Cocatalyst as a suspension with 1 to 40% by weight, preferably with 5 to 20% by weight in an aliphatic, inert suspending agent such as n-decane, hexane, heptane, diesel oil with a solution of the metallocene in an inert solvent such as toluene, hexane, Heptane, dichloromethane or with the finely ground solid of the metallocene is brought together. Conversely, a solution of the metallocene can also be used the solid of the cocatalyst are implemented.

The reaction is carried out by intensive mixing, for example by stirring at a molar Al / M ¹ ratio of 100/1 to 10000/1, preferably from 100/1 to 3000/1 and a reaction time from 5 to 120 minutes, preferably 10 to 60 Minutes, particularly preferably 10 to 30 minutes under inert conditions.

In the course of the reaction time to produce the supported catalyst system occur especially when using the metallocenes according to the invention with absorption maxima changes in the color of the reaction mixture in the visible range on the course of which the progress of the reaction can be followed.

After the reaction time has elapsed, the supernatant solution is separated off, for example by filtration or decanting. The remaining solid becomes 1 to 5 times with an inert suspending agent such as toluene, n-decane, hexane, diesel oil, dichloromethane to remove soluble components in the catalyst formed, in particular for the removal of unreacted and thus soluble metallocene, washed.

The supported catalyst system thus produced can be dried in vacuo as Powder or solvent still resuspended and as a suspension in one of the aforementioned inert suspending agents in the polymerization system be dosed.

According to the invention, instead of or in addition to an aluminoxane, compounds of the formulas R ¹⁸ _x NH _4-x BR ¹⁹ ₄ , R ¹⁸ _x PH _4-x BR ¹⁹ ₄ , R ¹⁸ ₃ CBR ¹⁹ ₄ , BR ¹⁹ _{3 can be used} as suitable cocatalysts. In these formulas, x is a number from 1 to 4, preferably 3, the radicals R ¹⁸ are the same or different, preferably the same, and are C ₁ -C ₁₀ alkyl, C ₆ -C ₁₈ aryl or form 2 radicals R ¹⁸ together with the atom connecting them a ring, and the radicals R ¹⁹ are the same or different, preferably the same, and represent C ₆ -C ₁₈ aryl, which can be substituted by alkyl, haloalkyl or fluorine.
In particular, R ^{18 represents} ethyl, propyl, butyl or phenyl and R ^{19 represents} phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (cf. EP 277 003, EP 277 004 and EP 426 638).

When using the above-mentioned cocatalysts, the actual (active) Polymerization catalyst from the reaction product of metallocene and one of the mentioned connections. This reaction product is therefore preferred first outside of the polymerization reactor in a separate step using a suitable solvent.

In principle, any compound is suitable as a cocatalyst according to the invention convert the neutral metallocene into a cation due to its Lewis acidity and this can stabilize ("unstable coordination"). In addition, the cocatalyst or the anion formed from it no further reactions with the formed Enter metallocene (see EP 427 697).

To remove catalyst poisons present in the olefin, cleaning is also necessary an aluminum alkyl, for example trimethyl aluminum or triethyl aluminum advantageous. This cleaning can take place both in the polymerization system itself, or the olefin is mixed with the Al compound before being added to the polymerization system brought into contact and then separated again.

The polymerization or copolymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more stages at a temperature of -60 to 200 ° C., preferably 30 to 80 ° C., particularly preferably 50 to 80 ° C. Olefins of the formula R ^a -CH = CH-R ^b are polymerized or copolymerized. In this formula, R ^a and R ^{b are the} same or different and represent a hydrogen atom or an alkyl radical having 1 to 14 carbon atoms. However, R ^a and R ^b can also form a ring with the C atoms connecting them. Examples of such olefins are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene or norbomadiene. In particular, propylene and ethylene are polymerized.

As a molecular weight regulator and / or to increase the activity, if necessary, Hydrogen added. The total pressure in the polymerization system is 0.5 to 100 bar. Polymerization in the technically particularly interesting is preferred Pressure range from 5 to 64 bar.

The metallocene is used in a concentration, based on the transition metal, of 10 ^-3 to 10 ^-8 , preferably 10 ^-4 to 10 ^-7 mol, of transition metal per dm ^{3 of} solvent or per dm ^{3 of} reactor volume. The aluminoxane is used in a concentration of 10 ^-5 to 10 ^-1 mol, preferably 10 ^-4 to 10 ^-2 mol per dm ³ solvent or per dm ³ reactor volume. The other cocatalysts mentioned are used in approximately equimolar amounts to the metallocene. In principle, however, higher concentrations are also possible.

If the polymerization is carried out as a suspension or solution polymerization becomes an inert solvent customary for the Ziegler low pressure process used. For example, one works in an aliphatic or cycloaliphatic Hydrocarbon; as such, for example, propane, butane, hexane, heptane, Isooctane, cyclohexane, methylcyclohexane. Furthermore, a petrol or hydrogenated diesel oil fraction can be used. Toluene can also be used. Is preferred polymerized in the liquid monomer.

If inert solvents are used, the monomers become gaseous or liquid added.

The duration of the polymerization is arbitrary, since that to be used according to the invention Catalyst system only a small time-dependent drop in the polymerization activity shows.

Before adding the catalyst, in particular the supported catalyst system (from a metallocene according to the invention and a supported cocatalyst or from a metallocene according to the invention and an organoaluminum compound on a polyolefin powder in finely divided form), another aluminum alkyl compound such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum can also be added or isoprenylaluminum can be added to the reactor to make the polymerization system inert (for example to separate catalyst poisons present in the olefin). This is added to the polymerization system in a concentration of 100 to 0.01 mmol Al per kg reactor content. Triisobutyl aluminum and triethyl aluminum are preferred in a concentration of 10 to 0.1 mmol Al per kg reactor content. As a result, the molar Al / M ¹ ratio can be chosen to be small in the synthesis of a supported catalyst system.

Basically, however, the use of other substances to catalyze the polymerization reaction not required, i.e. the systems according to the invention can be used as sole catalysts for olefin polymerization can be used.

The inventive method is characterized in that the described Metallocenes in the technically particularly interesting temperature range from 50 to 80 ° C with high catalyst activity polymers with very high molecular weight, in the case produce prochiral monomers of very high molecular weight and very high stereotacticity.

In particular, the zirconocenes according to the invention are characterized in that in the case of stereospecific polymerization of prochiral olefins, for example from Propylene, polymers with high isotaxy can be obtained.

In particular, in the case of isospecific polymerization of propylene, one obtains isotactic polypropylene with high isotactic sequence lengths and high Melting point.

In addition, with the supported catalyst systems according to the invention Avoided reactor coatings.

The following examples are intended to explain the invention in more detail.

All glassware was heated in vacuo and flushed with argon. All operations were in the absence of moisture and oxygen in Schlenk vessels carried out. The solvents used were fresh over under argon Na / K alloy distilled and stored in Schlenk vessels.

The Al / CH ₃ ratio in the aluminoxane was determined by decomposing the sample with H ₂ SO ₄ and determining the volume of the hydrolysis gases formed under normal conditions, and by complexometric titration of the aluminum in the then dissolved sample according to Schwarzenbach.

For Examples Nos. 3 to 5 with the supported aluminum compound (methylaluminoxane on silica gel), hereinafter referred to as "MAO on SiO ₂ ", an approx. 10% by weight suspension in n-decane was produced, which according to aluminum determination 60 mg Al / cm ³ contained.

For Examples 26 to 30 with the supported aluminum compound (methylaluminoxane on silica gel SD 3216-30 / Grace), hereinafter referred to as "FMAO on SiO ₂ ", a solvent-free powder was used which contained 20% by weight of aluminum in the solid.

Toluene-soluble methylaluminoxane was used as a 10% strength by weight toluene solution for the examples of suspension polymerization and bulk polymerization with unsupported metallocene and, according to aluminum determination, contained 36 mg Al / cm ³ . The mean degree of oligomerization according to freezing point depression in benzene was n = 20. A ratio Al: CH ₃ = 1: 1.55 was determined for the toluene-soluble methylalumoxane.

VZ =

Viskositätszahl in cm³/g

M_w =

Molmassengewichtsmittel in g/mol (ermittelt durch Gelpermeationschromatographie)

M_w/M_n =

Molmassendispersität

Schmp. =

Schmelzpunkt in °C (ermittelt mit DSC, 20°C/min Aufheiz-/Abkühlgeschwindigkeit)

II =

Isotaktischer Index (II = mm + 1/2 mr, ermittelt durch ¹³C-NMR-Spektroskopie)

MFI 230/5

Schmelzindex, gemessen nach DIN 53735; in dg/min

SD =

Polymerschüttdichte in g/dm³.

It means:

VZ =

Viscosity number in cm ³ / g

M _w =

Molar mass weight average in g / mol (determined by gel permeation chromatography)

M _w / M _n =

Molar mass dispersity

Mp =

Melting point in ° C (determined with DSC, 20 ° C / min heating / cooling rate)

II =

Isotactic index (II = mm + 1/2 mr, determined by ¹³ C NMR spectroscopy)

MFI 230/5

Melt index, measured according to DIN 53735; in dg / min

SD =

Polymer bulk density in g / dm ³ .

Synthesis of the metallocenes I used in the polymerization examples (the ones used Educts are commercially available):

A. rac-dimethylsilyl-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride (5) 1. (±) -2- (2-phenylbenzyl) propionic acid (1).

48.6 g (0.279 mol) of diethyl methylmalonate were added dropwise to 6.5 g (0.285 mol) of sodium in 160 cm ^{3 of} H ₂ O-free EtOH. 70.4 g (0.285 mol) of 2-phenylbenzylbromide in 20 cm ^{3 of} H ₂ O-free EtOH were then added dropwise and the mixture was heated to reflux for 3 h. The solvent was removed and the residue was mixed with 200 cm ³ H ₂ O. The organic phase was separated, the aqueous phase was saturated with NaCl and extracted twice with 200 cm ³ Et ₂ O each time. The organic phase combined with the extracts was dried (MgSO ₄ ).

¹H-NMR (100 MHz, CDCl₃): 11,7 (s, 1H, COOH), 7,1-7,5 (m, 9H, arom. H), 2,3 - 3,2 (m, 3H, CH u. CH₂), 0,9 (d, 3H, CH₃).

The residue which remained after the solvent had been stripped off was taken up in 500 cm ^{3 of} EtOH and 50 cm ^{3 of} H ₂ O, and 56 g (1 mol) of KOH were added. The reaction mixture was refluxed for 4 hours. The solvent was removed in vacuo, the residue was taken up in 500 cm ³ H ₂ O and acidified to pH 1 with concentrated aqueous HCl. The precipitate which had separated out was filtered off with suction and heated to 250 ° C. in the bulb tube for 30 min with vigorous foaming. 58.3 g (85%) 1 were obtained as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 11.7 (s, 1H, COOH), 7.1-7.5 (m, 9H, aromatic H), 2.3 - 3.2 (m, 3H, CH and CH ₂ ), 0.9 (d, 3H, CH ₃ ).

2. (±) -2-methyl-4-phenyl-indan-1-one (2)

A solution of 58 g (0.242 mol) 1 in 60 cm ³ (0.83 mol) thionyl chloride was stirred at room temperature for 18 h. Excess thionyl chloride was removed at 10 mbar and the oily residue was freed from adhering residues of thionyl chloride by repeatedly dissolving in 100 cm ^{3 of} toluene and stripping in vacuo.

¹H-NMR (100 MHz, CDCl₃): 7,2-7,8 (m, 8H, arom. H), 3,3 (dd, 1H, β-H), 2,5 - 2,9 (m, 2H, α- und β-H), 1,3 (d, 3H, CH₃).

The acid chloride was taken up in 150 cm ^{3 of} toluene and added dropwise at 10 ° C. to a suspension of 48 g (0.363 mol) of AlCl ₃ in 400 cm ^{3 of} toluene. After the addition was complete, the mixture was heated under reflux for a further 3 h. The reaction mixture was poured onto 500 g of ice and acidified to pH 1 with concentrated aqueous HCl. The organic phase was separated off and the aqueous phase was extracted ³ times with 100 cm ³ Et ₂ O each time. The combined organic phases were washed with saturated aqueous NaHCO ₃ , saturated aqueous NaCl solution and then dried (MgSO ₄ ). 50.4 g (93%) 2 were obtained, which was reacted further without further purification.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.2-7.8 (m, 8H, aromatic H), 3.3 (dd, 1H, β-H), 2.5 - 2.9 ( m, 2H, α - and β-H), 1.3 (d, 3H, CH ₃ ).

3. 2-methyl-7-phenyl-indene (3)

¹H-NMR (100 MHz, CDCl₃): 7,0-7,6 (m, 8H, arom. H), 6,5 (m, 1H, H- C(3)), 3,4 (s, 2H, CH₂), 2,1 (s, 3H, CH₃).

50 g (0.226 mol) 2 were dissolved in 450 cm ^{3 of} THF / MeOH (2: 1) and 12.8 g (0.34 mol) of sodium borohydride were added in portions at 0 ° C. while stirring and stirring was continued for 18 h. The reaction mixture was poured onto ice, concentrated HCl was added to pH 1 and extracted several times with Et ₂ O. The combined organic phases were washed with saturated aqueous NaHCO ₃ , NaCl solution and then dried (MgSO ₄ ). The solvent was removed in vacuo and the crude product was taken up in 1 dm ^{3 of} toluene without further purification, 2 g of p-toluenesulfonic acid were added and the mixture was heated under reflux for 2 h. The reaction mixture was washed with 200 cm ^{3 of} saturated aqueous NaHCO ₃ solution and the solvent was removed in vacuo. The crude product was purified by filtration over 500 g of silica gel (hexane / CH ₂ Cl ₂ ). 42 g (90%) 3 were obtained as a colorless oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0-7.6 (m, 8H, aromatic H), 6.5 (m, 1H, H-C (3)), 3.4 (s , 2H, CH ₂ ), 2.1 (s, 3H, CH ₃ ).

4. Dimethylbis (2-methyl-4-phenyl-indenyl) silane (4)

¹H-NMR (100 MHz, CDCl₃): 7,10 - 7,70 (m, 16H, arom. H), 6,80 (m, 2H, H-C(3)), 3,80 (s, 2H, H-C(1)), 2,20 (m, 6H, CH₃), -0,20 (m, 6H, CH₃Si).

A solution of 15 g (72.7 mmol) 3 in 200 cm ³ H ₂ O- and O ₂ -free toluene and 10 cm ³ H ₂ O- and O ₂ -free THF were mixed at room temperature under argon with 29 cm ³ ( 73 mmol) of a 2.5 M solution of butyllithium in hexane and heated to 80 ° C. for 1 h. The mixture was then cooled to 0 ° C. and 4.7 g (36.4 mmol) of dimethyldichlorosilane were added. The mixture was heated to 80 ° C. for 1 h and then poured onto 100 cm ³ H ₂ O. It was extracted several times with Et ₂ O and the combined organic phases were dried (MgSO ₄ ). The crude product which remained after the solvent had been stripped off in vacuo was chromographed on 300 g of silica gel (hexane / CH ₂ Cl ₂ ). 12.0 g (70%) 4 were obtained.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.10 - 7.70 (m, 16H, aromatic H), 6.80 (m, 2H, HC (3)), 3.80 (s, 2H) , HC (1)), 2.20 (m, 6H, CH ₃ ), -0.20 (m, 6H, CH ₃ Si).

5.rac-dimethylsilylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride (5)

¹H-NMR (300 MHz, CDCl₃): 7,0 - 7,7 (m, 16H, arom. H), 6,9 (s, 2H, H- C(3)), 2,2 (s, 6H, CH₃), 1,3 (m, 6H, CH₃Si).
Molmasse: 626 M⁺, korrektes Zerfallsmuster.

A solution of 6.0 g (12.9 mmol) 4 in 100 cm ³ H ₂ O- and O ₂ -free toluene was dissolved under argon at room temperature with 10.6 cm ³ (26 mmol) of a 2.5 M solution of Butyllithium added in hexane and heated to reflux for 3 h. The suspension of the dilithio salt was then cooled to -25 ° C. and 3.2 g (13.6 mmol) of zirconium tetrachloride were added. The mixture was warmed to room temperature within 1 h, stirred for a further 1 h and then filtered through a G3 frit. The residue was extracted with 50 cm ^{3 of} toluene and the combined filtrates were freed from the solvent in vacuo using an oil pump. 9.0 g of the metallocene were obtained as a mixture of the racemic and meso forms in a ratio of 1: 1 in the form of a yellow powder. The pure racemate (5) could be obtained by stirring the raw mixture several times with 20 cm ^{3 of} methylene chloride, the racemate remaining as a yellow crystal powder and the meso form being washed out. 2.74 g (33%) of the pure racemate were obtained.

¹ H-NMR (300 MHz, CDCl ₃ ): 7.0 - 7.7 (m, 16H, aromatic H), 6.9 (s, 2H, H-C (3)), 2.2 (s , 6H, CH ₃ ), 1.3 (m, 6H, CH ₃ Si).
Molar mass: 626 M ⁺ , correct decay pattern.

Example B rac-methylphenylsilanediylbis- (2-methyl-4-phenylindenyl) zirconium dichloride (7) 1. methylphenylbis- (2-methyl-4-phenylindenyl) silane (6)

¹H-NMR (100 MHz, CDCl₃): 7,0 - 7,8 (m, 16H, arom. H), 6,9 (m, 2H, H- C(3)), 3,9 (m, 2H, H-C(1)), 2,3 (m, 6H, CH₃), -0,1(s, 3H, CH₃Si).

A solution of 10.3 g (50 mmol) 3 in 90 ml H ₂ O- and O ₂ -free toluene and 10 ml H ₂ O- and O ₂ -free THF were mixed with 21 ml (52 mmol ) a 2.5 M solution of butyllithium in hexane was added and the mixture was heated at 80 ° C. for 1 h. The mixture was then cooled to 0 ° C. and mixed with 4.8 g (25 mmol) of methylphenyldichlorosilane and stirring was continued at RT overnight. The precipitated LiCl was separated off by filtration and the crude product which remained after the solvent had been stripped off in vacuo was chromatographed on 300 g of silica gel (hexane / CH ₂ Cl ₂ 9: 1). 4.6 g (35%) 6 were obtained.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 - 7.8 (m, 16H, aromatic H), 6.9 (m, 2H, H-C (3)), 3.9 (m , 2H, HC (1)), 2.3 (m, 6H, CH ₃ ), -0.1 (s, 3H, CH ₃ Si).

2. rac-methylphenylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride (7)

¹H-NMR (100 MHz, CDCl₃): 7,0 - 8,2 (m, 21H, arom. H), 6,9 (m, 2H, H-C(3)), 2,4 (s, 3H, CH₃), 2,0 (s, 3H, CH₃), 1,3 (s, 3H, CH₃Si). Massenspektrum: 690 M⁺, korrektes Zerfallsmuster.

2.3 g (4.4 mmol) 6 in 25 ml H ₂ O- and O ₂ -free toluene were mixed at room temperature under argon with 3.6 ml (8.9 mmol) of a 2.5 M solution of butyllithium in Hexane added and heated to 80 ° C for 3h. The suspension of the dilithio salt was then cooled to -30 ° C. and 1.1 g (4.5 mmol) of zirconium tetrachloride were added. The mixture was warmed to room temperature within 1 h and stirred for a further 1 h. After filtration through a G3 frit, the solvent of the filtrate was removed and the residue was crystallized from 10 ml of methylene chloride. 0.2 g of the racemic form of 7 was obtained as orange crystals.

¹ H NMR (100 MHz, CDCl ₃ ): 7.0 - 8.2 (m, 21H, aromatic H), 6.9 (m, 2H, HC (3)), 2.4 (s, 3H) , CH ₃ ), 2.0 (s, 3H, CH ₃ ), 1.3 (s, 3H, CH ₃ Si). Mass spectrum: 690 M ⁺ , correct decay pattern.

Example C rac-dimethylsilanediylbis (4-phenylindenyl) zirconium dichloride (12) 1. 3- (2-phenylphenyl) propionic acid (8)

¹H-NMR (100 MHz, CDCl₃): 9,1 (s, 1H, COOH), 6,9 - 7,5 (m, 9H, arom. H), 2,3 - 3,0 (m, 4H, 2 CH₂).

93 cm ³ (0.61 mmol) of diethyl malonate dissolved in 50 cm ^{3 of} H ₂ O-free EtOH were added dropwise to 14 g (0.61 mmol) of sodium in 400 cm ³ H ₂ O-free EtOH at room temperature. 150 g (0.61 mmol) of 2-phenylbenzyl bromide in 200 cm ^{3 of} H ₂ O-free EtOH were then added dropwise and the mixture was heated under reflux for 3 h. 102 g (1.83 mol) of KOH dissolved in 150 cm ^{3 of} H ₂ O were added at room temperature and the mixture was heated under reflux for a further 4 h. The solvents were removed in vacuo, the residue was mixed with H ₂ O until the solution was complete, and concentrated aqueous. HCl acidified to pH 1. The precipitate was filtered off, dried and heated at 130 ° C for 1 h. 112 g (81%) 8 were obtained as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 9.1 (s, 1H, COOH), 6.9 - 7.5 (m, 9H, aromatic H), 2.3 - 3.0 (m, 4H, 2 CH ₂ ).

2. 4-phenyl-1-indanone (9)

A solution of 102 g (0.45 mol) 8 in 37 cm ³ (0.5 mol) thionyl chloride was stirred at room temperature for 18 h. Excess thionyl chloride was removed at 10 mbar and the oily residue was freed from adhering residues of thionyl chloride by repeatedly dissolving in 100 cm ^{3 of} toluene and stripping in vacuo.

¹H-NMR (100 MHz, CDCl₃): 6,9 - 7,5 (m, 8H, arom. H), 2,5 - 3,4 (m, 4H, 2 CH₂).

The acid chloride was taken up in 200 cm ^{3 of} toluene and added dropwise at 10 ° C. to a suspension of 72 g (0.54 mol) of AlCl ₃ in 1000 cm ^{3 of} toluene and heated to 80 ° C. for 1 h. The reaction mixture was poured onto 1000 g of ice and concentrated with. aq. HCl acidified to pH 1. The organic phase was separated and the aq. Phase extracted ³ times with 200 cm ³ Et ₂ O each. The combined organic phases were washed with saturated aq. NaHCO ₃ -, saturated aq. Washed NaCl solution and then dried (MgSO ₄ ). 96 g (96%) 9 were obtained, which was reacted further without further purification.

¹ H-NMR (100 MHz, CDCl ₃ ): 6.9 - 7.5 (m, 8H, aromatic H), 2.5 - 3.4 (m, 4H, 2 CH ₂ ).

3. 7-phenyl-indene (10)

A solution of 86 g (0.41 mol) 9 in 300 cm ³ THF / methanol 2: 1 was mixed with 23 g (0.62 mol) NaBH ₄ in portions at 0 ° C. and stirred at room temperature for 18 h. The reaction mixture was poured onto 300 g of ice, with conc. aq. HCl added to pH 1 and extracted several times with Et ₂ O. The combined organic phases were washed with saturated aq. NaHCO ₃ -, saturated aq. Washed NaCl solution, dried (MgSO ₄ ) and freed from solvent in vacuo.

¹H-NMR (100 MHz, CDCl₃): 7,1 - 7,7 (m, 8H, arom. H), 6,9 und 6,5 (2m, 2H, CH), 3,5 (m, 2H, CH₂).

The crude product was taken up in 1000 cm ^{3 of} toluene, 4.5 g of p-toluenesulfonic acid were added and the mixture was heated to reflux on a water separator for 2 h. The reaction mixture was 3 times with 250 cm ³ saturated aq. Washed NaHCO ₃ solution and the solvent removed in vacuo. After distillation at 0.1 mbar, 33 g (41%) 10 was obtained as a colorless oil at 96-108 ° C.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.1-7.7 (m, 8H, aromatic H), 6.9 and 6.5 (2m, 2H, CH), 3.5 (m, 2H, CH ₂ ).

4. Dimethylbis (4-phenylindenyl) silane (11)

¹H-NMR (100 MHz, CDCl₃): 7,0 - 7,7 (m, 18H, arom. H und H-C(3)), 6,8 (dd, 2H, H-C(2)), 3,8 (m, 2H, H-C(1)), -0,2, (s, 6H, CH₃Si).

A solution of 10 g (50 mmol) 10 in 100 cm ³ H ₂ O- and O ₂ -free toluene and 5 ml H ₂ O- and O ₂ -free THF were mixed at room temperature with 18.7 cm ³ (50 mmol) a 20% solution of butyllithium in toluene and heated at 80 ° C for 2 h. The yellow suspension was then cooled to 0 ° C. and 3.2 g (25 mmol) of dimethyldichlorosilane were added. The reaction mixture was heated at 80 ° C. for a further hour and then washed with 50 cm ³ H ₂ O. The solvent was removed in vacuo and the residue was recrystallized from heptane at -20 ° C. 6.7 g (62%) 11 were obtained as colorless crystals (mp. 109-110 ° C.).

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 - 7.7 (m, 18H, aromatic H and HC (3)), 6.8 (dd, 2H, HC (2)), 3, 8 (m, 2H, HC (1)), -0.2, (s, 6H, CH ₃ Si).

5. rac-dimethylsilanediylbis (4-phenylindenyl) zirconium dichloride (12)

A solution of 6.6 g (16 mmol) 11 in 70 cm ³ H ₂ O- and O ₂ -free Et ₂ O was made under argon at room temperature with 12 cm ³ (32 mmol) of a 20% solution of butyllithium in toluene added and then heated to reflux for 3 h. The solvent was removed in vacuo and the residue was filtered with 50 ml of H ₂ O and O ₂ free hexane through a G3 Schlenk frit, washed with 50 ml of H ₂ O and O ₂ free hexane and dried (0.1 mbar , RT).

¹H-NMR (100 MHz, CDCl₃); 7,0 - 7,8 (m, 22 H, arom. H und H-C(3)), 6,1 (d, 2H, H-C(2)), 1,1 (s, 6H, CH₃Si). Massenspektrum: 598 M⁺, korrektes Zerfallsmuster.

The dilithio salt was added at -78 ° C to a suspension of 3.6 g (16 mmol) of zirconium tetrachloride in 80 cm ^{3 of} methylene chloride and over the course of 18 h under magn. Stirring warmed to room temperature. The mixture was filtered through a G3 frit and the residue was extracted in portions with a total of 200 cm ^{3 of} methylene chloride. The combined filtrates were freed from the solvent in vacuo and recrystallized from methylene chloride / hexane (1: 1). 5.6 g of the racemic and meso forms were obtained in a 1: 1 ratio. The racemic complex was obtained in the form of yellow crystals by recrystallization from methylene chloride.

¹ H NMR (100 MHz, CDCl ₃ ); 7.0 - 7.8 (m, 22 H, aromatic H and HC (3)), 6.1 (d, 2H, HC (2)), 1.1 (s, 6H, CH ₃ Si). Mass spectrum: 598 M ⁺ , correct decay pattern.

Example D rac-dimethylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dichloride (17) 1. (±) -2- (2-phenylbenzyl) butyric acid (13)

¹H-NMR (100 MHz, CDCl₃): 10,3 (s, 1H, COOH), 7,0 - 7,3 (m, 9 H, arom. H), 2,5 - 3,0 (m, 3H, CH und CH₂), 1,5 - 1,9 (m, 2H, CH₂), 0,9 (t, 3H, CH₃).

188 g (1 mol) of ethyl malonate dissolved in 100 cm ^{3 of} H ₂ O-free EtOH were added dropwise to 23 g (1 mol) of sodium in 400 cm ³ H ₂ O-free EtOH at room temperature. Then 247 g (1 mol) of 2-phenylbenzyl bromide in 300 cm ^{3 of} H ₂ O-free EtOH were added dropwise and the mixture was heated under reflux for 3 h. 170 g (3 mol) of KOH dissolved in 300 cm ^{3 of} H ₂ O were added at room temperature and the mixture was heated under reflux for a further 4 h. The solvent was removed in vacuo, the residue was mixed with H ₂ O until completely dissolved and then with concentrated aq. HCl acidified to pH 1. The precipitate was filtered off, dried and heated at 130 ° C for 1 h. 236 g (93%) 13 were obtained as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 10.3 (s, 1H, COOH), 7.0 - 7.3 (m, 9 H, aromatic H), 2.5 - 3.0 (m , 3H, CH and CH ₂ ), 1.5 - 1.9 (m, 2H, CH ₂ ), 0.9 (t, 3H, CH ₃ ).

2. (±) -2-ethyl-4-phenyl-1-indanone (14)

A solution of 236 g (0.93 mol) 13 in 81 cm ³ (1.2 mol) thionyl chloride was stirred at room temperature for 18 h. Excess thionyl chloride was removed at 10 mbar and the oily residue was freed from adhering residues of thionyl chloride by repeated dissolving in 200 cm ^{3 of} toluene and removal in vacuo.

The acid chloride was taken up in 400 cm ^{3 of} toluene and added dropwise at 10 ° C. to a suspension of 133 g (1.0 mol) of AlCl ₃ in 2000 cm ^{3 of} toluene and heated to 80 ° C. for 1 h. The reaction mixture was poured onto 2000 g of ice and concentrated with. aq. HCl acidified to pH 1. The organic phase was separated and the aq. Phase extracted ³ times with 200 cm ³ Et ₂ O each. The combined organic phases were washed with saturated aq. NaHCO ₃ -, saturated aq. Washed NaCl solution and then dried (MgSO ₄ ).

¹H-NMR (100 MHz, CDCl₃): 7,0 - 7,8 (m, 8 H, arom. H), 3,1 - 3,4 (m, 1H, H-C(3)), 2,5 - 2,9 (m, 2H, H-C(2) und H-C(3)), 1,3 - 2,0 (m, 2H, CH₂), 0,9 (t, 3H, CH₃).

187 g (85%) 14 were obtained, which was reacted further without further purification.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 - 7.8 (m, 8 H, aromatic H), 3.1 - 3.4 (m, 1H, HC (3)), 2, 5-2.9 (m, 2H, HC (2) and HC (3)), 1.3-2.0 (m, 2H, CH ₂ ), 0.9 (t, 3H, CH ₃ ).

3. 2-ethyl-7-phenylindene (15)

8 g (0.21 mol) of NaBH _{4 were} added in portions to a solution of 50 g (0.21 mol) 14 in 600 cm ^{3 of} THF / methanol 2: 1 at 0 ° C. and the mixture was stirred at room temperature for 18 h. The reaction mixture was poured onto 600 g of ice, with conc. aq. HCl added to pH 1 and extracted several times with Et ₂ O. The combined organic phases were washed with saturated aq. NaHCO ₃ -, saturated aq. Washed NaCl solution and then dried (MgSO ₄ ).

¹H-NMR (100 MHz, CDCl₃): 7,0 - 7,5 (m, 8H, arom. H), 6,5 (m, 1H, CH), 3,2 (m, 2H, CH₂), 2,5 (dq, 2H, CH₂), 1,1 (t, 3H, CH₃).

The crude product was taken up in 1000 cm ^{3 of} toluene, 4.5 g of p-toluenesulfonic acid were added and the mixture was heated to reflux on a water separator for 2 h. The reaction mixture was 3 times with 250 cm ³ saturated aq. Washed NaHCO ₃ solution and the solvent removed in vacuo. After distillation at 0.1 mbar, 33 g (72%) 15 were obtained as a colorless oil at 135 ° C.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 - 7.5 (m, 8H, aromatic H), 6.5 (m, 1H, CH), 3.2 (m, 2H, CH ₂ ), 2.5 (dq, 2H, CH ₂ ), 1.1 (t, 3H, CH ₃ ).

4. Dimethylbis (2-ethyl-4-phenylindenyl) silane (16)

¹H-NMR (100 MHz, CDCl₃): 6,9 - 7,4 (m, 16H, arom. H), 6,5 (m, 2H, H-C(3)), 3,7 (m, 2H, H-C(1)), 2,4 (m, 4H, CH₂), 1,1 (t, 6H, CH₃), -0,1, (s, 6H, CH₃Si).

A solution of 17 g (77 mmol) 15 in 160 cm ³ H ₂ O- and O ₂ -free toluene and 8 ml H ₂ O- and O ₂ -free THF were mixed with 29 cm ³ (77 mmol) a 20 % solution of butyllithium in toluene and heated to 80 ° C for 2 h. The yellow suspension was then cooled to 0 ° C. and 5 g (38 mmol) of dimethyldichlorosilane were added. The reaction mixture was heated at 80 ° C. for a further 1 h and then washed with 100 cm ³ H ₂ O. The solvent was removed in vacuo and the residue was purified by chromatography on 200 g of silica gel (hexane / methylene chloride 9: 1). 9 g (47%) 16 were obtained as a viscous oil.

¹ H NMR (100 MHz, CDCl ₃ ): 6.9-7.4 (m, 16H, aromatic H), 6.5 (m, 2H, HC (3)), 3.7 (m, 2H) , HC (1)), 2.4 (m, 4H, CH ₂ ), 1.1 (t, 6H, CH ₃ ), -0.1, (s, 6H, CH ₃ Si).

5. rac-dimethylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dichloride (17)

A solution of 5.6 g (11 mmol) 16 in 50 cm ³ H ₂ O- and O ₂ -free Et ₂ O was mixed with 8.4 cm ^{3 of} a 20% solution of butyllithium in toluene under argon at room temperature and then heated to reflux for 3 h. The solvent was removed in vacuo and the residue was filtered with 50 ml of H ₂ O and O ₂ free hexane through a G3 Schlenk frit, washed with 50 ml of H ₂ O and O ₂ free hexane and dried (0.1 mbar , RT).

¹H-NMR (100 MHz, CDCl₃): 6,8 - 7,7 (m, 16 H, arom. H), 6,6 (m, 2H, H-C(3)), 2,3-3,9 (m, 4H, CH₂), 1,0 - 1,4 (m, 12H, CH₃ und CH₃Si). Massenspektrum: 654 M⁺, korrektes Zerfallsmuster.

The dilithio salt was added to a suspension of 2.5 g (11 mmol) of zirconium tetrachloride in 50 cm ^{3 of} methylene chloride at -78 ° C. and under magn. Stirring warmed to room temperature. The mixture was filtered through a G3 frit and the residue was extracted in portions with a total of 100 cm ^{3 of} methylene chloride. The combined filtrates were freed from the solvent in vacuo and recrystallized from toluene / hexane (1: 1). 2 g (27%) of the racemic and meso forms were obtained in a 1: 1 ratio. The recrystallization from toluene gave racemic complex 17 in the form of yellow crystals.

¹ H-NMR (100 MHz, CDCl ₃ ): 6.8 - 7.7 (m, 16 H, aromatic H), 6.6 (m, 2H, HC (3)), 2.3-3, 9 (m, 4H, CH ₂ ), 1.0-1.4 (m, 12H, CH ₃ and CH ₃ Si). Mass spectrum: 654 M ⁺ , correct decay pattern.

Example E rac-dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride (24) 1. 2- (1-naphthyl) toluene (18)

13.9 g (0.57 mol) of magnesium shavings were overlaid with 150 ml of H ₂ O-free Et ₂ O and the Grignard reaction was started with 5 g of 2-bromotoluene and a few granules of iodine. 93 g (0.57 mol) of 1-bromotoluene in 450 ml of H ₂ O-free Et ₂ O were then added dropwise in such a way that the reaction mixture was kept at the boil. After the addition was complete, the mixture was heated to boiling until the magnesium had completely reacted.

¹H-NMR (100 MHz, CDCl₃): 7,2 - 8,0 (m, 11H, arom. H), 2,0 (s, 3H, CH₃).

The Grignard solution was then added dropwise to a solution of 118 g (0.57 mol) of 1-bromonaphthalene and 3.5 g of bis (triphenylphosphine) nickel dichloride in 800 cm ^{3 of} toluene, so that the internal temperature did not exceed 50.degree. The mixture was then heated under reflux for 3 h, with 500 ml of 10% aq. HCI added, the phases separated and the organic phase freed from solvent in vacuo. After filtration over silica gel (hexane), 115 g (92%) 18 were obtained as a colorless oil.

¹ H NMR (100 MHz, CDCl ₃ ): 7.2-8.0 (m, 11H, aromatic H), 2.0 (s, 3H, CH ₃ ).

2. 2- (1-naphthyl) benzyl bromide (19)

¹H-NMR (100 MHz, CDCl₃): 7,1 - 8,0 (m, 11H, arom. H), 4,2 (q, 2H, CH₂Br).

114 g (0.52 mol) of 18 and 103 g (0.58 mol) of N-bromosuccinimide were dissolved in 2000 cm ^{3 of} carbon tetrachloride at room temperature, 3 g of azobisisobutyronitrile were added and the mixture was heated under reflux for 4 h. The precipitated succinimide was filtered off, the solvent was removed in vacuo and the residue was purified by filtration over 1000 g of silica gel (hexane / methylene chloride 9: 1). 141 g (82%) 19 were obtained as a colorless, tear-irritating oil.

¹ H NMR (100 MHz, CDCl ₃ ): 7.1-8.0 (m, 11H, aromatic H), 4.2 (q, 2H, CH ₂ Br).

3. (±) -2 (2- (1-naphthyl) benzyl) propionic acid (20)

¹H-NMR (100 MHz, CDCl₃): 10,1 (s, 1H, COOH), 6,9 - 8,0 (m, 11H, arom. H), 2,3 - 3,0 (m, 3H, CH₂ und CH), 0,8 (d, 3H, CH₃).

75 g (0.43 mmol) of diethyl methylmalonate dissolved in 50 cm ^{3 of} H ₂ O-free EtOH were added dropwise to 10 g (0.43 mmol) of sodium in 100 cm ³ H ₂ O-free EtOH at room temperature. Then 140 g (0.43 mmol) of 2-phenylbenzyl bromide in 200 cm ³ H ₂ O-free EtOH were added dropwise and the mixture was heated under reflux for 3 h. 85 g (1.3 mol) of KOH dissolved in 100 cm ^{3 of} H ₂ O were added at room temperature and the mixture was heated under reflux for a further 4 h. The solvents were removed in vacuo, the residue was mixed with H ₂ O until the solution was complete, and concentrated aqueous. HCl acidified to pH 1. The precipitate was filtered off, dried and heated at 130 ° C for 1 h. 96 g (77%) 20 were obtained as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 10.1 (s, 1H, COOH), 6.9 - 8.0 (m, 11H, aromatic H), 2.3 - 3.0 (m, 3H, CH ₂ and CH), 0.8 (d, 3H, CH ₃ ).

4. (±) -2-methyl-4- (1-naphthyl) -1-indanone (21)

A solution of 96 g (0.33 mol) of 20 in 37 cm ³ (0.5 mol) of thionyl chloride was stirred at room temperature for 18 h. Excess thionyl chloride was removed at 10 mbar and the oily residue was freed from adhering residues of thionyl chloride by repeatedly dissolving in 100 cm ^{3 of} toluene and stripping in vacuo.

¹H-NMR (100 MHz, CDCl₃): 7,3 - 8,0 (m, 10H, arom. H), 2,2 - 3,2 (m, 3H, CH₂ und CH), 1,2 (d, 3H, CH₃).

The acid chloride was taken up in 200 cm ^{3 of} toluene and added dropwise at 10 ° C. to a suspension of 44 g (0.33 mol) of AlCl ₃ in 1000 cm ^{3 of} toluene and heated to 80 ° C. for 3 hours. The reaction mixture was poured onto 1000 g of ice and concentrated with. aq. HCl acidified to pH 1. The organic phase was separated and the aq. Phase extracted ³ times with 200 cm ^{3 of} methylene chloride each. The combined organic phases were washed with saturated aq. NaHCO ₃ -, saturated aq. Washed NaCl solution and then dried (MgSO ₄ ). After chromatography on 1000 g of silica gel (hexane / methylene chloride), 12 g (13%) 21 were obtained.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.3 - 8.0 (m, 10H, aromatic H), 2.2 - 3.2 (m, 3H, CH ₂ and CH), 1.2 (d, 3H, CH ₃ ).

5. 2-methyl-7- (1-naphthyl) indene (22)

1.3 g (33 mmol) of NaBH _{4 were} added to a solution of 12 g (44 mmol) of 21 in 100 cm ^{3 of} THF / methanol 2: 1 at 0 ° C. and the mixture was stirred at room temperature for 18 h. The reaction mixture was poured onto 100 g of ice, with conc. aq. HCl added to pH 1 and extracted several times with Et ₂ O. The combined organic phases were washed with saturated aq. NaHCO ₃ -, saturated aq. Washed NaCl solution and then dried (MgSO ₄ ).

¹H-NMR (100 MHz, CDCl₃): 7,0 - 8,0 (m, 10H, arom. H), 6,6 (m, 1H, CH), 3,0 (m, 2H, CH₂), 2,0 (m, 3H, CH₃).

The crude product was taken up in 200 cm ^{3 of} toluene, 0.5 g of p-toluenesulfonic acid was added and the mixture was heated to reflux on a water separator for 2 h. The reaction mixture was 3 times with 50 cm ³ saturated aq. Washed NaHCO ₃ solution and the solvent removed in vacuo. After filtration through 200 g of silica gel (hexane / methylene chloride), 10 g (86%) 22 were obtained as a colorless oil.

¹ H NMR (100 MHz, CDCl ₃ ): 7.0 - 8.0 (m, 10H, aromatic H), 6.6 (m, 1H, CH), 3.0 (m, 2H, CH ₂ ), 2.0 (m, 3H, CH _3).

6. Dimethylbis (2-methyl-4- (1-naphthyl) indenyl) silane (23)

¹H-NMR (100 MHz, CDCl₃): 7,2 - 8,1 (m, 20H, arom. H), 6,4 (m, 2H, H-C(3)), 4,0 (m, 2H, H-C(1)), -0,1, (s, 6H, CH₃Si).

A solution of 10 g (38 mmol) 22 in 100 cm ³ H ₂ O- and O ₂ -free toluene and 5 ml H ₂ O- and O ₂ -free THF were mixed at room temperature with 14.4 cm ³ (50 mmol) a 20% solution of butyllithium in toluene and heated at 80 ° C for 2 h. The yellow suspension was then cooled to 0 ° C. and 2.5 g (19 mmol) of dimethyldichlorosilane were added. The reaction mixture was heated at 80 ° C. for a further hour and then washed with 50 cm ³ H ₂ O. The solvent was removed in vacuo and the residue was recrystallized from heptane at -20 ° C. 8.2 g (75%) 23 were obtained as colorless crystals.

¹ H NMR (100 MHz, CDCl ₃ ): 7.2 - 8.1 (m, 20H, aromatic H), 6.4 (m, 2H, HC (3)), 4.0 (m, 2H) , HC (1)), -0.1, (s, 6H, CH ₃ Si).

7. rac-dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride (24)

A solution of 8.0 g (14 mmol) 23 in 70 cm ³ H ₂ O- and O ₂ -free Et ₂ O was added under argon at room temperature with 10.5 cm ^{3 of} a 20% solution of butyllithium in toluene and then heated to reflux for 3 h. The solvent was removed in vacuo and the residue was filtered with 50 ml of H ₂ O and O ₂ free hexane through a G3 Schlenk frit, washed with 50 ml of H ₂ O and O ₂ free hexane and dried (0.1 mbar , RT).

¹H-NMR (100 MHz, CDCl₃): 7,0 - 8,0 (m, 22 H, arom. H), 6,5 (s, 2H, H-C(3)), 2,2 (s, 6H, CH₃), 1,3 (s, 6H, CH₃Si). Massenspektrum: 729 M⁺, korrektes Zerfallsmuster.

The dilithio salt was added to a suspension of 3.2 g (14 mmol) of zirconium tetrachloride in 80 cm ^{3 of} methylene chloride at -78 ° C. and under magn. Stirring warmed to room temperature. The mixture was filtered through a G3 frit and the residue was extracted in portions with a total of 400 cm ^{3 of} methylene chloride. The combined filtrates were freed from the solvent in vacuo and recrystallized from methylene chloride. 1.5 g (15%) of the racemic and meso forms were obtained in a 1: 1 ratio. The racemic complex was obtained in the form of yellow crystals by recrystallization from methylene chloride.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 - 8.0 (m, 22 H, aromatic H), 6.5 (s, 2H, HC (3)), 2.2 (s, 6H, CH ₃ ), 1.3 (s, 6H, CH ₃ Si). Mass spectrum: 729 M ⁺ , correct decay pattern.

Example F rac-dimethylsilanediylbis (2-methyl-4- (2-naphthyl) indenyl) zirconium dichloride (31) 1. 2- (2-naphthyl) toluene (25)

14 g (0.57 mol) of magnesium shavings were covered with 150 ml of H ₂ O-free Et ₂ O and the Grignard reaction started with 5 g of 2-bromotoluene and a few granules of iodine. 95 g (0.58 mol) of bromotoluene in 450 ml of H ₂ O-free Et ₂ O were then added dropwise in such a way that the reaction mixture was kept at the boil. After the addition was complete, the mixture was heated to boiling until the magnesium had completely reacted.

¹H-NMR (100 MHz, CDCl₃): 7,0 - 7,9 (m, 11H, arom. H), 1,9 (s, 3H, CH₃).

The Grignard solution was then added dropwise to a solution of 120 g (0.57 mol) of 2-bromonaphthalene and 3.5 g of bis (triphenylphosphine) nickel dichloride in 800 cm ^{3 of} toluene, so that the internal temperature did not exceed 50.degree. The mixture was then heated under reflux for 3 h, with 500 ml of 10% aq. HCI added, the phases separated and the organic phase freed from solvent in vacuo. After filtration over silica gel (hexane), 107 g (87%) 25 were obtained as a colorless oil.

¹ H NMR (100 MHz, CDCl ₃ ): 7.0 - 7.9 (m, 11H, aromatic H), 1.9 (s, 3H, CH ₃ ).

2. 2- (2-naphthyl) benzyl bromide (26)

¹H-NMR (100 MHz, CDCl₃): 6,9 - 8,0 (m, 11H, arom. H), 4,1 (s, 2H, CH₂Br).

105 g (0.48 mol) of 25 and 90 g (0.5 mol) of N-bromosuccinimide were dissolved in 2000 cm ^{3 of} carbon tetrachloride at room temperature, 3 g of azobisisobutyronitrile were added and the mixture was heated under reflux for 4 h. The precipitated succinimide was filtered off, the solvent was removed in vacuo and the residue was purified by filtration over 1000 g of silica gel (hexane / methylene chloride 9: 1). 112 g (79%) 26 were obtained as a colorless, tear-irritating oil.

¹ H NMR (100 MHz, CDCl ₃ ): 6.9-8.0 (m, 11H, aromatic H), 4.1 (s, 2H, CH ₂ Br).

3. (±) -2- (2- (2-naphthyl) benzyl) propionic acid (27)

¹H-NMR (100 MHz, CDCl₃): 10,9 (s, 1H, COOH), 7,0 - 8,1 (m, 11 H, arom. H), 2,3 - 3,0 (m, 3H, CH₂ und CH), 1,0 (d, 3H, CH₃).

70 g (0.37 mmol) of diethyl methylmalonate dissolved in 50 cm ^{3 of} H ₂ O-free EtOH were added dropwise to 8.5 g (0.37 mmol) of sodium in 100 cm ³ H ₂ O-free EtOH. 110 g (0.37 mmol) of 26 in 200 cm ^{3 of} H ₂ O-free EtOH were then added dropwise and the mixture was heated under reflux for 3 h. 62 g (1.1 mol) of KOH dissolved in 100 cm ^{3 of} H ₂ O were added at room temperature and the mixture was heated under reflux for a further 4 h. The solvents were removed in vacuo, the residue was mixed with H ₂ O until the solution was complete, and concentrated aqueous. HCl acidified to pH 1. The precipitate was filtered off, dried and heated at 130 ° C for 1 h. 90 g (84%) 27 were obtained as a viscous oil.

¹ H-NMR (100 MHz, CDCl ₃ ): 10.9 (s, 1H, COOH), 7.0 - 8.1 (m, 11 H, aromatic H), 2.3 - 3.0 (m , 3H, CH ₂ and CH), 1.0 (d, 3H, CH ₃ ).

4. (±) -2-methyl-4- (2-naphthyl) -1-indanone (28)

A solution of 89 g (0.31 mol) 27 in 37 cm ³ (0.5 mol) thionyl chloride was stirred at room temperature for 18 h. Excess thionyl chloride was removed at 10 mbar and the oily residue was freed from adhering residues of thionyl chloride by repeatedly dissolving in 100 cm ^{3 of} toluene and stripping in vacuo.

¹H-NMR (100 MHz, CDCl₃): 7,1 - 8,0 (m, 10H, arom. H), 2,2 - 3,3 (m, 3H, CH₂ und CH), 1,1 (d, 3H, CH₃).

The acid chloride was taken up in 200 cm ^{3 of} toluene and added dropwise at 10 ° C. to a suspension of 44 g (0.33 mol) of AlCl ₃ in 1000 cm ^{3 of} toluene and heated to 80 ° C. for 3 hours. The reaction mixture was poured onto 1000 g of ice and concentrated with. aq. HCl acidified to pH 1. The organic phase was separated and the aq. Phase extracted ³ times with 200 cm ^{3 of} methylene chloride each. The combined organic phases were washed with saturated aq. NaHCO ₃ -, saturated aq. Washed NaCl solution and then dried (MgSO ₄ ). After chromatography on 1000 g of silica gel (hexane / AeOEt), 27 g (33%) 28 were obtained.

¹ H NMR (100 MHz, CDCl ₃ ): 7.1-8.0 (m, 10H, aromatic H), 2.2-3.3 (m, 3H, CH ₂ and CH), 1.1 (d, 3H, CH ₃ ).

5. 2-methyl-7- (2-naphthyl) indene (29)

3.8 g (100 mmol) of NaBH _{4 were} added to a solution of 27 g (100 mmol) of 28 in 200 cm ^{3 of} THF / methanol 2: 1 at 0 ° C. and the mixture was stirred at room temperature for 18 h. The reaction mixture was poured onto 100 g of ice, with conc. aq. HCl added to pH 1 and extracted several times with Et ₂ O. The combined organic phases were washed with saturated aq. NaHCO ₃ -, saturated aq. Washed NaCl solution and then dried (MgSO ₄ ).

¹H-NMR (100 MHz, CDCl₃): 7,0 - 8,0 (m, 10H, arom. H), 6,6 (m, 1H, CH), 3,0 (m, 2H, CH₂), 2,0 (m, 3H, CH₃).

The crude product was taken up in 500 cm ^{3 of} toluene, 1.5 g of p-toluenesulfonic acid were added and the mixture was heated to reflux on a water separator for 2 h. The reaction mixture was 3 times with 50 cm ³ saturated aq. Washed NaHCO ₃ solution and the solvent removed in vacuo. After filtration over 200 g of silica gel (hexane / methylene chloride), 18.4 g (72%) 29 were obtained as a colorless oil.

¹ H NMR (100 MHz, CDCl ₃ ): 7.0 - 8.0 (m, 10H, aromatic H), 6.6 (m, 1H, CH), 3.0 (m, 2H, CH ₂ ), 2.0 (m, 3H, CH _3).

6. Dimethylbis (2-methyl-4- (2-naphthyl) indenyl) silane (30)

¹H-NMR (100 MHz, CDCl₃): 7,0 - 8,1 (m, 20H, arom. H), 6,4 (m, 2H, H-C(3)), 4,0 (m, 2H, H-C(1)), -0,1, (s, 6H, CH₃Si).

A solution of 18 g (70 mmol) 29 in 70 cm ³ H ₂ O- and O ₂ -free toluene and 4 ml H ₂ O- and O ₂ -free THF were mixed with 26 cm ³ (70 mmol) of a 20 % solution of butyllithium in toluene and heated to 80 ° C for 2 h. The yellow suspension was then cooled to 0 ° C. and 4.5 g (35 mmol) of dimethyldichlorosilane were added. The reaction mixture was heated at 80 ° C. for a further hour and then washed with 50 cm ³ H ₂ O. The solvent was removed in vacuo and the residue was recrystallized from heptane at -20 ° C. 10.8 g (54%) 30 were obtained as colorless crystals.

¹ H NMR (100 MHz, CDCl ₃ ): 7.0-8.1 (m, 20H, aromatic H), 6.4 (m, 2H, HC (3)), 4.0 (m, 2H) , HC (1)), -0.1, (s, 6H, CH ₃ Si).

7. rac-dimethylsilanediylbis (2-methyl-4- (2-naphthyl) indenyl) zirconium dichloride (31)

A solution of 10.5 g (18 mmol) 30 in 70 cm ³ H ₂ O- and O ₂ -free Et ₂ O was added under argon at room temperature with 13.6 cm ^{3 of} a 20% solution of butyllithium in toluene and then heated to reflux for 3 h. The solvent was removed in vacuo and the residue was filtered with 50 ml of H ₂ O and O ₂ free hexane through a G3 Schlenk frit, washed with 50 ml of H ₂ O and O ₂ free hexane and dried (0.1 mbar , RT).

¹H-NMR (100 MHz, CDCl₃): 7,0 - 8,0 (m, 22 H, arom. H), 6,9 (s, 2H, H-C(3)), 2,2 (s, 6H, CH₃), 1,3 (s, 6H, CH₃Si). Massenspektrum: 729 M⁺, korrektes Zerfallsmuster.

The dilithio salt was added at -78 ° C to a suspension of 4.2 g (18 mmol) of zirconium tetrachloride in 80 cm ^{3 of} methylene chloride and over the course of 18 h under magn. Stirring warmed to room temperature. The mixture was filtered through a G3 frit and the residue was extracted in portions with a total of 400 cm ^{3 of} methylene chloride. The combined filtrates were freed from the solvent in vacuo and recrystallized from methylene chloride. 3.1 g (23%) of the racemic and meso forms were obtained in a 1: 1 ratio. The racemic complex was obtained in the form of yellow crystals by recrystallization from methylene chloride.

¹ H-NMR (100 MHz, CDCl ₃ ): 7.0 - 8.0 (m, 22 H, aromatic H), 6.9 (s, 2H, HC (3)), 2.2 (s, 6H, CH ₃ ), 1.3 (s, 6H, CH ₃ Si). Mass spectrum: 729 M ⁺ , correct decay pattern.

Example G rac-ethanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride (33) 1. 1,2-bis (2-methyl-4-phenylindenyl) ethane (32)

¹H-NMR (100 MHz, CDCl₃): 7,0 - 8,1 (m, 20H, arom. H), 6,4 (m, 2H, H-C(3)), 4,0 (m, 2H, H-C(1)), -0,1, (s, 6H, CH₃Si).

A solution of 50 g (0.24 mol) 3 in 500 ml THF was mixed with 90 cm ³ (0.24 mol) of a 20% solution of butyllithium in toluene under argon at room temperature and stirred at 60 ° C. for 2 h. It was cooled to -78 ° C., 22.5 g (0.12 mol) of 1,2-dibromoethane were added and the mixture was warmed to room temperature in the course of 18 h. The reaction mixture was washed with 50 cm ³ H ₂ O, the solvent was removed in vacuo and the residue was chromatographed on 500 g silica gel (hexane / methylene chloride 9: 1). 2.5 g (5%) 32 were obtained as a yellow oil which slowly solidified at -20 ° C.

¹ H NMR (100 MHz, CDCl ₃ ): 7.0-8.1 (m, 20H, aromatic H), 6.4 (m, 2H, HC (3)), 4.0 (m, 2H) , HC (1)), -0.1, (s, 6H, CH ₃ Si).

2. rac-ethanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride (33)

A solution of 2.3 g (5 mmol) 32 in 20 ml H ₂ O- and O ₂ -free Et ₂ O was added under argon at room temperature with 4 cm ³ (10 mmol) of a 20% solution of butyllithium in toluene and heated to reflux for 3 hours. The solvent was removed in vacuo and the residue was filtered with 30 ml of H ₂ O and O ₂ free hexane through a G3 Schlenk frit, washed with 30 ml of H ₂ O and O ₂ free hexane and dried (0.1 mbar , RT).

¹H-NMR (100 MHz, CDCl₃): 7,0 - 7,7 (m, 16H, arom. H), 6,6 (m, 2H, H-C(3)), 3,4-4,1 (m, 4H, H₂C-CH₂), 2,1 (s, 6H, CH₃). Massenspektrum: 598 M⁺, korrektes Zerfallsmuster.

The dilithio salt was added at -78 ° C to a suspension of 1.2 g (5 mmol) of zirconium tetrachloride in 30 cm ^{3 of} methylene chloride and over the course of 18 h under magn. Stirring warmed to room temperature. The mixture was filtered through a G3 frit and the residue was extracted in portions with a total of 100 cm ^{3 of} methylene chloride. The combined filtrates were freed from the solvent in vacuo and recrystallized from methylene chloride / hexane. 0.5 g (18%) of the racemic and meso forms were obtained in a 1: 1 ratio. The racemic complex was obtained in the form of yellow crystals by recrystallization from toluene.

¹ H NMR (100 MHz, CDCl ₃ ): 7.0-7.7 (m, 16H, aromatic H), 6.6 (m, 2H, HC (3)), 3.4-4.1 (m, 4H, H ₂ C-CH ₂ ), 2.1 (s, 6H, CH ₃ ). Mass spectrum: 598 M ⁺ , correct decay pattern.

Example H Me ₂ Si (2-Me-4-Ph-Indenyl) ₂ ZrMe [BPh ₄ ] (35) 1. rac-dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dimethyl (34)

0.5 g (0.8 mmol) rac-5 was dissolved in 10 cm ³ H ₂ O and O ₂ -free Et ₂ O at -30 ° C with 1 cm ^{3 of} a 1.6 M (1.6 mmol) Solution of methyl lithium in Et ₂ O was added and the mixture was stirred at 0 ° C. for 1 h. The solvent was then removed in vacuo, the residue was taken up in 20 cm ³ H ₂ O and O ₂ -free hexane and filtered through a G3 frit. 0.34 g (72%) 34 was obtained. Mass spectrum: 588 M ⁺ , correct decay pattern.

2. Me ₂ Si (2-Me-4-Ph-Indenyl) ₂ ZrMe [BPh ₄ ] (35)

0.2 g (0.3 mmol) 34 were added at 0 ° C to 0.25 g (mmol) tributylammonium tetraphenylborate in 30 cm ³ toluene. The mixture was heated to 50 ° C. with stirring and the mixture was stirred at this temperature for 15 minutes. An aliquot of the solution was used for the polymerization.

example 1

A dry 16 dm ³ reactor was first flushed with nitrogen and then with propylene and filled with 10 dm ^{3 of} liquid propylene. Then 30 cm ^{3 of} toluene methylaluminoxane solution were added and the mixture was stirred at 30 ° C. for 15 minutes.

In parallel, 1.1 mg of rac-5 were dissolved in 20 cm ^{3 of} toluene solution of methylaluminoxane (27 mmol of Al) and reacted by standing for 15 minutes. The solution was then added to the reactor, heated to the polymerization temperature of 50 ° C. by supplying heat (4 ° C./min) and the polymerization system was kept at 50 ° C. for 1 hour by cooling. The polymerization was stopped by adding 20 cm ^{3 of} isopropanol. The excess monomer was vented and the polymer was dried in vacuo. 0.9 kg of polypropylene were obtained. The reactor showed thin deposits on the inner wall and stirrer. The catalyst activity was 818 kg PP / g metallocene x h. VZ = 905 cm ³ / g; Mp = 159.4 ° C; II = 98.8%; mmmm = 95.4%; M _w = 1100000 g / mol; M _w / M _n = 2.5.

Example 2

The polymerization from Example 1 was repeated, with the difference that 0.9 mg of rac-5 was used as the catalyst and the polymerization temperature was 70.degree. 1.4 kg of polypropylene were obtained. The reactor showed heavy deposits on the inner wall and stirrer. The catalyst activity was 1555 kg PP / g metallocene x h. VZ = 719 cm ³ / g; Mp = 157.7 ° C.

Example 3

22 cm ^{3 of} the suspension of the "MAO on SiO ₂ " (49 mmol Al) was introduced into a G3 Schlenk frit under argon and mixed with a solution of 4.5 mg rac-5 in 10 cm ³ toluene (7.2 μmol Zr ) offset.
The reaction mixture was stirred at room temperature for 30 minutes, during which time a spontaneous color change to red gradually faded. The mixture was then filtered and the solid was washed 3 times with 10 cm ^{3 of} hexane. The remaining, hexane-moist filter residue was resuspended in 20 cm ^{3 of} hexane for the polymerization.

In parallel, a dry 16 dm ³ reactor was flushed first with nitrogen and then with propylene and filled with 10 dm ^{3 of} liquid propylene.
Then 3 cm ^{3 of} triisobutylaluminum (pure, 12 mmol) were diluted with 30 cm ^{3 of} hexane, added to the reactor and the mixture was stirred at 30 ° C. for 15 minutes.
The catalyst suspension was then added to the reactor, heated to the polymerization temperature of 50 ° C. (4 ° C./min) and the polymerization system was kept at 50 ° C. for 1 hour by cooling. The polymerization was stopped by adding 20 cm ^{3 of} isopropanol. The excess monomer was vented and the polymer was dried in vacuo.
The result was 300 g of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 67 kg PP / g metallocene x h. VZ = 1380 cm ³ / g; Mp = 156 ° C.

Example 4

The synthesis of the supported catalyst system from Example 3 was repeated with the difference that 13 cm ³ (29 mmol Al) of the suspension "MAO on SiO ₂ " and 1.8 mg rac-5 (2.9 μmol Zr) were used.

The polymerization was carried out analogously to Example 3 at 70 ° C. 420 g of polypropylene powder resulted. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 233 kg PP / g metallocene x h. VZ = 787 cm ³ / g; Mp = 149.5 ° C.

Example 5

The synthesis of the supported catalyst system from Example 3 was repeated with the difference that 150 cm ³ (335 mmol Al) of the suspension "MAO on SiO ₂ " and 44.2 mg rac-5 (70.3 μmol Zr) were used and that Reaction mixture was stirred at room temperature for 60 minutes. The solid was then filtered off and washed 3 times with 50 cm ^{3 of} hexane. The remaining, hexane-moist filter residue was dried in vacuo to a free-flowing, pale pink powder. 33.3 g of supported, dry catalyst were obtained.

For the polymerization, 2.98 g (4 mg = 6.3 μmol Zr) of this dry catalyst were resuspended in 20 cm ^{3 of} hexane.

The polymerization was carried out analogously to Example 3 at 70 ° C.
The result was 1.05 kg of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity was 263 kg PP / g metallocene x h. VZ = 944 cm ³ / g; Mp = 156 ° C.

Example 6

A dry 1.5 dm ³ reactor was flushed with N ₂ and filled at 20 ° C. with 750 cm ^{3 of} a dearomatized gasoline cut with the boiling range 100-120 ° C. ("®Exxsol 100/120"). Then the gas space of the reactor was flushed nitrogen-free by pressing 8 bar propylene 5 times and relaxing. Then 3.75 cm ^{3 of} toluene solution of methylaluminoxane (10% by weight of MAO) were added. The contents of the reactor were heated to 30 ° C. in the course of 15 minutes with stirring and the total pressure was adjusted to 8 bar by adding propylene at a stirring speed of 500 rpm.

In parallel, 0.1 mg rac-5 was dissolved in 1.25 cm ³ toluene methylaluminoxane solution and brought to a complete reaction by standing for 15 minutes. The solution was then added to the reactor, the polymerization system brought to a temperature of 50 ° C. and kept at this temperature for 1 h by appropriate cooling. The pressure was kept at 8 bar during this time by appropriate addition of propylene, then the reaction was stopped by adding 2 cm ^{3 of} isopropanol, the polymer was filtered off and dried in vacuo.

16 g of polypropylene were obtained. The reactor showed deposits on the inner wall and stirrer. The catalyst activity (KZA _red ) was 20 kg PP / g metallocene xhx bar. VZ = 833 cm ³ / g; Mp = 159 ° C.

Example 7

The polymerization from Example 6 was repeated with the difference that the Polymerization temperature was 60 ° C.

35 g of polypropylene were obtained. The reactor showed deposits on the inner wall and stirrer. The catalyst activity (KZA _red ) was 44 kg PP / g metallocene xhx bar. VZ = 484 cm ³ / g; Mp = 159 ° C.

Example 8

The polymerization from Example 6 was repeated with the difference that the Polymerization temperature was 70 ° C.

88 g of polypropylene were obtained. The reactor showed deposits on the inner wall and stirrer. The catalyst activity (KZA _red ) was 110 kg PP / g metallocene xhx bar. VZ = 414 cm ³ / g; Mp = 159 ° C.

Examples 9-12

The procedure was as in Example 2. However, hydrogen was metered in before filling with liquid propylene: example Ndm ² H ₂ Metallocene activity VZ [kgPP / gMet * h] [cm ³ / g] 9 1.5 1640 495 10 3rd 1590 212 11 4.5 1720 142 12th 200 1580 17th

Examples 9-12 show the good hydrogen responsiveness of the invention Metallocens. It is a molecular weight control down to the wax area (see example 12) possible.

Example 13

The procedure was as in Example 3. However, before the catalyst was added, 0.2 bar of hydrogen was pressed onto the reactor, and the polymerization temperature was 60 ° C. However, ethylene was metered in uniformly during the polymerization. A total of 12 g of ethylene was added to the reactor. 0.4 kg of ethylene-propylene copolymer were obtained. The metallocene activity was 88 kg copolymer / g metallocene x h. The ethylene content in the polymer was 2.4% by weight, the ethylene was predominantly incorporated in isolation. VZ = 200 cm ³ / g; Melting point 143 ° C.

Example 14

The procedure was as in Example 13. However, a total of 34 g of ethylene were metered in during the polymerization. 0.38 kg of ethylene-propylene copolymer with 7% by weight of ethylene were obtained. VZ = 120 cm ³ / g; Melting point 121 ° C.

Example 15

The procedure was as in Example 4. However, 4 g of ethylene were metered in during the polymerization and 0.1 bar of hydrogen was injected before the polymerization. 0.52 kg of ethylene-propylene copolymer was obtained. The metallocene activity was 286 kg copolymer / g metallocene x h. The ethylene content in the polymer was 6.1% by weight, the majority of the ethylene was incorporated in isolation. VZ = 150 cm ³ / g; Melting point 116 ° C.

Example 16

A dry 150 dm ³ reactor was flushed with nitrogen and filled at 20 ° C. with 80 dm ^{3 of} a dearomatized gasoline cut with a boiling range of 100-120 ° C.

Then the gas space was flushed nitrogen-free by pressing 2 bar propylene 5 times and relaxing. After adding 50 l of liquid propylene. 64 cm ^{3 of} toluene methylaluminoxane solution (corresponding to 100 mmol Al, molar mass according to cryoscopic determination 1080 g / mol) are added and the reactor contents are heated to 50.degree. A hydrogen content in the gas space of the reactor of 2.0% was set by metering in hydrogen and later kept constant during the first polymerization stage by subsequent metering.

9.8 mg of rac-7 were dissolved in 32 ml of the toluene solution of methylaluminoxane (corresponding to 50 mmol of Al) and added to the reactor after 15 minutes. The polymerization was then carried out in a first polymerization stage at 50 ° C. for 5 hours. The mixture was then vented to a reactor pressure of 3 bar and 2000 g of ethylene gas were fed in. The reactor pressure rose to 8 bar and polymerization was continued at 40 ° C. for a further 14 h before the reaction was stopped with CO ₂ gas.
18.6 kg block copolymer were obtained, corresponding to a metallocene activity of 99.9 kg copolymer / g metallocene x h. VZ = 230cm ³ / g; MFI (230/5) = 11dg / min, MFI (230 / 2.16) = 3.7 dg / min; Melting point of the polymer of the 1st polymer stage: 159 ° C, glass transition temperature of the polymer of the 2nd polymer stage: -38 ° C. The block copolymer contained 5% ethylene. Fractionation of the product gave the following composition: 69% by weight homopolymer, 31% by weight copolymer, the copolymer having an ethylene content of 15% by weight, the average block length C ₂ being 2.2.

Example 16 a

The procedure was as in Example 16.

3 mg rac-24 were dissolved in 32 ml of the toluene methylaluminoxane solution (corresponding to 50 mmol Al) and added to the reactor after 15 minutes. The polymerization was then carried out in a first polymerization stage at 50 ° C. for 2.5 hours. The mixture was then vented to 3 bar reactor pressure and 3000 g of ethylene gas were fed. The reactor pressure rose to 8 bar and polymerization was carried out at 40 ° C. for a further 8 h before the reaction was stopped with CO ₂ gas.

16.5 kg block copolymer were obtained, corresponding to a metallocene activity of 524 kg copolymer / g metallocene x h. VZ = 480 cm ³ / g; MFI (230/5) = 2 dg / min, melting point of the polymer of the 1st polymer stage: 162 ° C, glass transition temperature of the polymer of the 2nd polymer stage: -54 ° C. The block polymer contained 15% ethylene.

Example 17

The procedure was as in Example 1. However, 12.5 mg of metallocene rac-7 were used. 1.5 kg of polypropylene were obtained, the metallocene activity was 120 kg PP / g of metallocene × h. VZ = 1050 cm ³ / g; Melting point 159 ° C.

Example 18

The procedure was as in Example 2. However, 4.1 mg of metallocene rac-7 were used. 1.3 kg of polypropylene were obtained and the metallocene activity was 317 kg of PP / g of metallocene × h. VZ = 555 cm ³ / g; Melting point 157 ° C.

Comparative Example A

The procedure was as in Example 1. However, 12.5 mg of rac-phenyl (methyl) silanediylbis (2-methyl-1-indenyl) zirconium dichloride were used. 1.35 kg of polypropylene were obtained, the metallocene activity was 108 kg PP / g of metallocene x h. VZ = 1050 cm ³ / g; Melting point 149 ° C.

Comparative Example B

The procedure was as in Example 1. However, 12.5 mg of rac-phenyl (methyl) silanediylbis (1-indenyl) zirconium dichloride were used. 0.28 kg of polypropylene were obtained and the metallocene activity was 22.4 kg of PP / g of metallocene × h. VZ = 74 cm ³ / g; Melting point 141 ° C.

Example 19

The procedure was as in Example 1. However, 3.3 mg 24 were used. 0.78 kg of polypropylene were obtained, the metallocene activity was 237 kg PP / g metallocene × h. VZ = 1700 cm ³ / g; Melting point 163 ° C, M _w = 2.1 * 10 ⁶ g / mol, MFI 230 / 21.6 = 1 dg / min; M _w / M _n = 2.1.

Example 19 a

The procedure was as in Example 2. However, 1.0 mg of rac-24 were used. 1.2 kg of polypropylene were obtained. The metallocene activity was 1200 kg PP / g metallocene x h. VZ = 1100 cm ³ / g. Melting point = 161 ° C.

Example 20

The procedure was as in Example 1; however, the polymerization temperature was 40 ° C. 6.0 mg 17 were used. 1.95 kg of polypropylene were obtained, the metallocene activity was 325 kg PP / g of metallocene x h. VZ = 1320 cm ³ / g; Melting point 162 ° C, M _w = 1.79 * 10 ⁶ g / mol, M _w / M _n = 2.3.

Comparative example C

The procedure was as in Example 20. However, the metallocene rac-dimethylsilanediylbis (2-ethyl-1-indenyl) zirconium dichloride which was not according to the invention was used. 0.374 kg of polypropylene were obtained, the metallocene activity was 62.3 kg PP / g of metallocene x h. VZ = 398 cm ³ / g; Melting point 147 ° C, M _w = 450,000 g / mol, M _w / M _n = 2.5.

Example 21

The procedure was as in Example 1. However, 5.2 mg 31 were used. 1.67 kg polypropylene were obtained, the metallocene activity was 321 kg PP / g metallocene x h. VZ = 980 cm ³ / g; Melting point 158 ° C.

Example 22

The procedure was as in Example 1, but the polymerization was carried out at 30 ° C. However, 3.7 mg of 33 were used. 0.35 kg of polypropylene were obtained and the metallocene activity was 94 kg of PP / g of metallocene × h. VZ = 440 cm ³ / g; Melting point 153 ° C.

Example 23

A dry 16 dm ³ reactor was rinsed with propylene and filled with 10 dm ³ liquid propylene. Then 1.1 cm ^{3 of} the reaction product from H.2 (corresponding to 7.5 mg 34) was dissolved in 20 cm ^{3 of} toluene and added to the reactor at 30 ° C. The reactor was heated to 50 ° C. (10 ° C./min) and the polymerization system was kept at this temperature for 1 hour by cooling. The polymerization was stopped by adding CO ₂ gas. The excess monomer was vented and the polymer was dried in vacuo at 80 ° C. 2.45 kg of polypropylene were obtained. VZ = 875 cm ³ / g; Melting point 160 ° C.

Example 24

A dry 16 dm ³ reactor was flushed with nitrogen and filled at 20 ° C. with 10 dm ^{3 of} a dearomatized gasoline cut with a boiling range of 100-120 ° C. Then the gas space of the reactor was flushed nitrogen-free by pressing 2 bar of ethylene 5 times and relaxing. Then 30 cm ^{3 of} toluene methylaluminoxane solution (corresponding to 45 mmol Al, molecular weight after cryoscopic determination 700 g / mol) were added. The contents of the reactor were heated to 30 ° C. in the course of 15 minutes with stirring, and the total pressure was adjusted to 5 bar by adding ethylene at a stirring speed of 250 rpm.

In parallel, 3.2 g 12 were dissolved in 20 cm ³ toluene methylaluminoxane solution and preactivated by standing for 15 minutes. The solution was then added to the reactor, the polymerization system was brought to a temperature of 50 ° C. and kept at this temperature for 4 hours by appropriate cooling. The total pressure was kept at 5 bar during this time by appropriate supply of ethylene.

The polymerization was stopped by adding 20 ml of isopropanol, the polymer was filtered off and dried in vacuo. 0.7 kg of polyethylene was obtained. VZ = 690 cm ³ / g.

Example 25

The procedure of Example 24 was followed. In deviation from Example 23, 1.8 mg rac-7 was used, the polymerization system was brought to 70 ° C. and kept at this temperature for 1 h. 0.9 kg of polyethylene was obtained. VZ = 730 cm ³ / g.

Example 26

15 g "F-MAO on SiO2" (111 mmol Al) were suspended in 100 cm ³ toluene in a stirrable vessel and cooled to -20 ° C. At the same time, 155 mg (0.246 mmol) of rac-5 were dissolved in 75 cm ^{3 of} toluene and added dropwise to the suspension within 30 minutes. The mixture was slowly warmed to room temperature with stirring, the suspension taking on a red color. The mixture was then stirred at 80 ° C. for one hour and, after cooling to room temperature, the mixture was filtered and the solid was washed ³ times with 100 cm ^{3 of} toluene and 1 time with 100 cm ^{3 of} hexane. The filtrate was red. The remaining, hexane-moist filter residue was dried in vacuo. 13.2 g of free-flowing, light red, supported catalyst were obtained. The analysis showed a content of 3.2 mg zirconocene per gram of catalyst.

Polymerization: For the polymerization, 2.08 g of the catalyst were suspended in 50 cm ^{3 of} a dearomatized gasoline cut with a boiling range of 100-120 ° C. The polymerization was carried out analogously to Example 3 at 60 ° C. 1100 g of polypropylene powder were obtained. The reactor showed no deposits on the inner wall or stirrer. Activity = 165 kg PP / (g metallocene xh). VZ = 1100 cm ³ / g. Melting point = 153 ° C; M _w = 1,485,000; M _w / M _n = 3.2; MFI 230/5 = 0.1 dg / min; SD = 440 g / dm ³ .

Example 27

1.31 g of the catalyst from Example 26 were suspended in 50 cm ^{3 of} a dearomatized gasoline cut with the boiling range 100-120 ° C. The polymerization was carried out analogously to Example 3 at 70 ° C. 1300 g of polypropylene powder were obtained. The reactor showed no deposits on the inner wall or stirrer. Activity = 310 kg PP / (g metallocene xh). VZ = 892 cm ³ / g; Melting point = 150 ° C, M _w = 1,290,000; M _w / M _n = 3.0; SD = 410 g / dm ³ .

Example 28

The support from Example 26 was repeated with the difference that 0.845 g of rac-5 dissolved in 500 cm ^{3 of} toluene was reacted with 90 g of "F-MAO on SiO ₂ " suspended in 500 cm ^{3 of} toluene. 84 g of red, powdery catalyst were obtained. The analysis showed a content of 9 mg metallocene per gram of solid, the red filtrate contained 13 mg zirconium.

Polymerization: 1.1 g of the supported catalyst were suspended in 50 ml of a dearomatized gasoline cut with the boiling range 100-120 ° C. The polymerization was carried out analogously to Example 3 at 70 ° C. 2850 g of polypropylene powder were obtained. The reactor showed no deposits on the inner wall or stirrer. Activity = 288 kg PP / (g metallocene xh); VZ = 638 cm ³ / g; Melting point = 150 ° C; MFI 230/5 = 0.5 dg / min; SD = 410 g / dm ³ .

Example 29

A microporous polypropylene powder (AKZO) having a particle size less than 100 μ m was freed by extraction with toluene in a Soxhlet extractor under inert conditions of impurities and then with 20 wt.% Strength trimethylaluminum solution in toluene is washed and dried in vacuo. In parallel, 51.1 mg of rac-5 were dissolved in 40 cm ^{3 of} toluene methylaluminoxane solution and brought to a complete reaction by standing for 15 minutes. 16.5 g of the PP powder were metered in and by briefly applying a vacuum, the gas in the pores of the support and part of the solvent were removed and the catalyst solution was completely absorbed. Intensive shaking of the reaction vessel gave 46 g of homogeneous, finely divided and well-flowing red powder. 10 g of the supported catalyst powder were prepolymerized under inert conditions in a rotary evaporator with ethylene for 30 minutes. The ethylene overpressure was kept constant at 0.1 bar by means of a pressure control valve, and the catalyst powder was mixed by continuously rotating the reaction vessel with cooling to 0 ° C. The result was 12 g of prepolymerized catalyst.

Polymerization: 4.6 g of the supported, prepolymerized catalyst were suspended in 50 cm ^{3 of} a dearomatized gasoline cut with the boiling range 100-120 ° C. The polymerization was carried out analogously to Example 3 at 70 ° C. The result was 250 g of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer, the average particle diameter was 1000 μm . Activity = 59 kg PP / (g metallocene xh); VZ = 734 cm ³ / g. Melting point = 152 ° C; SD = 390 g / dm ³ .

Example 30

1 g of the supported, unpolymerized catalyst from Example 29 was suspended in 50 cm ^{3 of} n-decane for the polymerization. The polymerization was carried out analogously to Example 3 at 70 ° C. 600 g of polypropylene resulted. The reactor showed thin deposits on the inner wall and stirrer, the average particle diameter was> 2000 μm . Activity = 540 kg PP / (g metallocene xh); VZ = 1400 cm ³ / g; melting point = 157.7 ° C; SD = 280 g / dm ³ .

Claims (12)

1. A catalyst formed from a metallocene of the formula I and a co-catalyst

   

   in which, in the formula I,

   M¹ is a metal from group IVb, Vb or VIb of the Periodic Table of the Elements,

   R¹ and R² are identical or different and are a hydrogen atom, a C₁-C₁₀-alkyl group, a C₁-C₁₀-alkoxy group, a C₆-C₁₀-aryl group, a C₆-C₁₀-aryloxy group, a C₂-C₁₀-alkenyl group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀-alkylaryl group, a C₈-C₄₀-arylalkenyl group, a OH group or a halogen atom,

   the radicals R³ are identical or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀-alkyl group, which may be halogenated, a C₆-C₁₀-aryl group, an NR¹⁶ ₂, -SR¹⁶, -OSiR¹⁶ ₃, -SiR¹⁶ ₃ or -PR¹⁶ ₂ radical, in which R¹⁶ is a halogen atom, a C₁-C₁₀-alkyl group or a C₆-C₁₀-aryl group,

   R⁴ to R¹² are identical or different and have the meanings mentioned for R³, or adjacent radicals R⁴ to R¹², together with the atoms connecting them, form one or more aromatic or aliphatic rings, or the radicals R⁵ and R⁸ or R¹², together with the atoms connecting them, form an aromatic or aliphatic ring,

   R¹³ is

   

   

   =BR¹⁴, =AIR¹⁴, -Ge-, -O-, -S-, =SO, =SO₂, =NR¹⁴, =CO, =PR¹⁴ or =P(O)R¹⁴, where R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀-alkyl group, a C₁-C₁₀-fluoroalkyl group, a C₁-C₁₀-alkoxy group, a C₆-C₁₀-aryl group, a C₆-C₁₀-fluoroaryl group, a C₆-C₁₀-aryloxy group, a C₂-C₁₀-alkenyl group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀-alkylaryl group, a C₈-C₄₀-arylalkenyl group, or R¹⁴ and R¹⁵, in each case together with the atoms connecting them, form one or more rings, and

   M² is silicon, germanium or tin.
2. A catalyst as claimed in claim 1, in which the cocatalyst is an aluminoxane.
3. A catalyst as claimed in claim 1 or 2, in which the metallocene has been applied to a support.
4. A catalyst as claimed in one or more of claims 1 to 3, in which the metallocene has been prepolymerized.
5. A polyolefin obtainable by polymerization or copolymerization of an olefin of the formula R^a-CH=CH-R^b, in which R^a and R^b are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or R^a and R^b, together with the atoms connecting them, may form one or more rings, at a temperature of from -60 to 200°C, at a pressure of from 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst as claimed in one or more of claims 1 to 4.
6. A process for the preparation of a metallocene of the formula I

   

   in which, in the formula I,

   M¹ is a metal from group IVb, Vb or VIb of the Periodic Table of the Elements,

   R¹ and R² are identical or different and are a hydrogen atom, a C₁-C₁₀-alkyl group, a C₁-C₁₀-alkoxy group, a C₆-C₁₀-aryl group, a C₆-C₁₀-aryloxy group, a C₂-C₁₀-alkenyl group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀-alkylaryl group, a C₈-C₄₀-arylalkenyl group, a OH group or a halogen atom,

   the radicals R³ are identical or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀-alkyl group, which may be halogenated, a C₆-C₁₀-aryl group, an NR¹⁶ ₂, -SR¹⁶, -OSiR¹⁶ ₃, -SiR¹⁶ ₃ or -PR¹⁶ ₂ radical, in which R¹⁶ is a halogen atom, a C₁-C₁₀-alkyl group or a C₆-C₁₀-aryl group,

   R⁴ to R¹² are identical or different and have the meanings mentioned for R³, or adjacent radicals R⁴ to R¹², together with the atoms connecting them, form one or more aromatic or aliphatic rings, or the radicals R⁵ and R⁸ or R¹², together with the atoms connecting them, form an aromatic or aliphatic ring,

   R¹³ is

   

   

   =BR¹⁴, =AIR¹⁴, -Ge-, -O-, -S-, =SO, =SO₂, =NR¹⁴, =CO, =PR¹⁴ or =P(O)R¹⁴, where R¹⁴ and R¹⁵ are identical or different and are a hydrogen atom, a halogen atom, a C₁-C₁₀-alkyl group, a C₁-C₁₀-fluoroalkyl group, a C₁-C₁₀-alkoxy group, a C₆-C₁₀-aryl group, a C₆-C₁₀-fluoroaryl group, a C₆-C₁₀-aryloxy group, a C₂-C₁₀-alkenyl group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀-alkylaryl group, a C₈-C₄₀-arylalkenyl group, or R¹⁴ and R¹⁵, in each case together with the atoms connecting them, form one or more rings, and

   M² is silicon, germanium or tin,

   comprising the following steps:

   a) reaction of a phenylbenzyl halide derivative of the formula A with substituted malonic acid esters under basic conditions to give a compound of the formula B

   

   b) saponification of the compound of the formula B using alkali metal hydroxide and decarboxylation by heat treatment to give a compound of the formula C

   

   c) reaction of the compound of the formula C with chlorinating reagents and subsequent cyclization by means of a Friedel-Crafts catalyst in an inert solvent to give a phenyl-1-indanone of the formula D

   

   d) reaction of the phenyl-1-indanone of the formula D with a hydride-transferring reagent and a corresponding catalyst in an inert solvent to give the corresponding alcohol, and conversion of this alcohol under acidic conditions into the 7-phenylindene derivatives of the formula E

   

   e) deprotonation of the compound of the formula E using a strong base in an inert solvent and reaction with a reagent of the formula X-R¹³-X, in which R¹³ is as defined in the formula I, and X is a nucleophilic leaving group, to give a bridged ligand system of the formula G

   

   f) deprotonation of the bridged ligand system of the formula G using two equivalents of a strong base in an inert solvent and reaction with a metal halide in a suitable solvent to give a metallocene of the formula H

   

   g) optionally subsequent derivatization using compounds R¹Li/R²Li can take place,

   where the radicals in the compounds of the formulae A, B, C, D, E, G, H, R¹Li and R²Li are as defined in the formula I.
7. An indanone of the formula D as defined in claim 6.
8. An indene of the formula E as defined in claim 6.
9. A bridged ligand system of the formula G as defined in claim 6.
10. The use of an indanone of the formula D as claimed in claim 7 for the preparation of a compound of the formula I as defined in claim 1.
11. The use of an indene of the formula E as claimed in claim 8 for the preparation of a compound of the formula I as defined in claim 1.
12. The use of a bridged ligand system of the formula G as claimed in claim 9 for the preparation of a compound of the formula I as defined in claim 1.